JP3479644B2 - Liquid bleaching detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a liquid bleaching detergent composition. In particular, it relates to a liquid bleach composition effective against black stains derived from bacteria and mold.

[0002]

2. Description of the Related Art Dirt on a hard surface of a house varies depending on the cleaning surface to be cleaned. Generally, stains composed of denatured oil and dust are likely to adhere around the kitchen stove, and for toilets and bathrooms, inorganic and organic substances form insoluble salts and become stains as they are,
Bacteria and molds may propagate and become dirt by using them as substrates. Among the stains on the hard surface, dark stains derived from these bacteria and molds are difficult to remove sufficiently with detergents containing surfactants and abrasives as main ingredients, so chlorine containing hypochlorite is used. A system bleaching detergent is used.

JP-A-57-61099 describes a liquid germicidal bleach composition containing hypochlorite and a quaternary ammonium type cationic activity and having excellent germicidal properties. The applicant of the present invention also discloses in Japanese Unexamined Patent Publication No. 7-82593 that a quaternary ammonium salt having a specific structural formula, an alkyl sulfate ester salt, a polyoxyalkylene alkyl sulfate ester salt, an alkylbenzene sulfonate salt and an amphoteric interface are added to hypochlorite. Disclosed is a liquid bleaching composition excellent in bleaching oil stains, which contains one or more selected from activators.

Conventional chlorine-based bleach cleaners have shown sufficient effects on tiles, joints and other dark stains.
Recently, in addition to tiles and joints, the number of cases where molds occur in resin parts such as silicone resin-based caulking and soft polyvinyl chloride resin-based packing used for joints between walls and bathtubs has increased, Even with the conventional bleaching detergents, which were sufficiently effective for tiles and joints, it was difficult to bleach and decompose and remove the molds generated in these resin parts. The applicants have found that it is effective to use a cleaning liquid in which a specific cationic activator and sodium hypochlorite are mixed against such stains. When a cleaning agent containing sodium chlorite is applied to stains on a specific plastic (ABS or polystyrene) where base material damage was observed, it causes problems such as cracking when the plastic is stressed. The drawback was that it was easy.

[0005]

The object of the present invention is to show an excellent bleaching detergency against mildew growing on a soft resin part,
Furthermore, it is to provide a liquid bleaching detergent composition having reduced damage to resins such as ABS and polystyrene.

[0006]

The present invention provides (a) an alkali metal hypochlorite salt [hereinafter referred to as (a) component] 0.5.
To 5.0% by mass, (b) quaternary ammonium type surfactant [hereinafter referred to as (b) component] 0.01 to 0.5% by mass, (c) alkali metal hydroxide [hereinafter, (c) Component)] 0.2-3.0 mass% and water, the total content of surfactants is 0.01-3.5 mass%, and [mass% of (a)] and [ Mass% of (b)] is 0.5
The following relates to a liquid bleaching detergent composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkali metal hypochlorite as the component (a) include sodium hypochlorite and potassium hypochlorite, and sodium hypochlorite is particularly preferable. (A) in the liquid bleaching detergent composition of the present invention
The content of the component is 0.5 to 5.0% by mass, preferably 1.0 to 4.0% by mass, more preferably 1.5 to 2.5.
It is in the range of mass%. The content of the component (a) is 0.5% by mass or more for obtaining a sufficient bleaching effect, a sufficient bleaching speed and bleaching power can be obtained, and if it is 5.0% by mass or less, good stability is obtained. can get.

The quaternary ammonium type surfactant as the component (b) preferably has at least one alkyl group having 6 to 16 carbon atoms, more preferably one represented by the following general formula (1). Is.

[0009]

[Chemical 1]

[Wherein R ¹ is an alkyl group having 6 to 16 carbon atoms, preferably 8 to 12 carbon atoms, and R ² and R ³ are each independently a methyl or ethyl group, preferably a methyl group, R ⁴ is a methyl group, an ethyl group or a benzyl group, preferably a methyl or benzyl group, particularly preferably a benzyl group. X ⁻ is a halogen ion or R ⁵ SO ₄ ^— , and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms. Of these, halogen ions are preferable as X ⁻ , and Cl ⁻ and Br ⁻ are more preferable. ].

The component (b), especially the quaternary ammonium type surfactant represented by the above general formula (1), is deficient in conventional chlorine-based bleaching detergents due to bacteria and mold to the resin system. It enhances the bleaching cleaning effect on stains, and it is thought that this is because the quaternary ammonium type surfactant assists the contact of the hypochlorite ion with the hydrophobic material.

The component (b) is contained in the liquid bleaching detergent composition of the present invention in an amount of 0.01 to 0.5% by mass, preferably 0.0.
It is contained in an amount of 5 to 0.3% by weight.

The alkali metal hydroxide of the component (c) of the present invention means a combination of an alkali metal ion and a hydroxy ion present in the liquid bleaching detergent composition, that is, a free alkali, and another counter ion. In case of the combination of, it is not counted. For example, when an organic acid is added separately, even if it is added as an alkali metal hydroxide, it does not count as an alkali metal hydroxide because it forms a counter ion of the organic acid. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and of these, sodium hydroxide is preferable. Generally with chlorine bleach, etc.,
In order to obtain the stability of hypochlorite, there is a tendency to add a large amount of alkali metal hydroxide. However, in the present invention, the component (c) is contained in the composition in an amount of 0.2 to 3.0% by mass, and preferably 0 to 3.0%, in order to obtain a sufficient effect particularly on mold-derived stains attached to the resin system. .2 to 1.0% by mass, and more preferably 0.3 to 0.8% by mass. In order to suppress the stability of hypochlorite and the damage to the substrate, the content of the component (c) is required to be 0.2% by mass or more, and if it is 3.0% by mass or less, ( In addition to the stability of the alkali metal hypochlorite as the component (a), the bleaching rate is appropriate, and a sufficient effect against mold stain on the resin can be obtained. In the present invention, the amount of component (c) in the composition is measured by the method described in ASTM D 2022-89. That is, this method measures the amount of free alkali in the bleaching agent as sodium hydroxide (NaOH), and in the present invention, the amount of free alkali in the composition obtained by this method is (C)
The amount of the ingredient.

By the way, as described above, the quaternary ammonium type surfactant facilitates the introduction of hypochlorite into a resin or the like, but care must be taken in its formulation.
For example, when the content of the alkali metal hypochlorite salt is relatively large, increasing the content of the quaternary ammonium type surfactant increases the tendency to damage the resin-based substrate. In this case, by reducing the compounding amount of the quaternary ammonium type surfactant, it becomes possible to obtain a sufficient bleaching power without damaging the substrate. On the other hand, when the concentration of alkali metal hypochlorite is low, a relatively large amount of quaternary ammonium type surfactant is added in order to suppress damage to the substrate and achieve a sufficient bleaching effect on the resin part. It is necessary. As a result of studying this point, we have found that it can be explained by the "product" of the blending amount of the component (a) and the blending amount of the component (b). That is, in order to suppress damage to the resin base material, the product of [mass% of component (a)] and [mass% of component (b)] is 0.5 or less, preferably 0.45 or less. It is necessary to blend.

The liquid bleaching detergent composition of the present invention has no influence on the storage stability and does not damage the resin-based substrate even when it is further contacted with hypochlorite for a long time.
(D) Amine oxide type surfactant having one or more alkyl groups having 8 to 16 carbon atoms [hereinafter referred to as (d) component]
It is preferable to contain

The component (d) used in the present invention has 8 carbon atoms.
The amine oxide type surfactant having one or more alkyl groups of 16 to 16 is preferably represented by the following general formula (2).

[0017]

[Chemical 2]

[In the formula, R ⁶ is an alkyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, and particularly preferably 10 to 14 carbon atoms. R ⁷ is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3. R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and an alkyl group is preferable from the viewpoint of storage stability. A is -COO-, -CONH-, -OCO-, -NHCO
It is a group selected from — and —O—, r is a number of 0 or 1, and r = 0 is particularly preferable from the viewpoint of storage stability. ].

The component (d) is preferably added to the composition in an amount of 0.
05-3.0 mass%, more preferably 0.05-2.0
A more excellent base material damage suppressing ability can be obtained by containing the material in an amount of 0.1% by mass, particularly preferably 0.05 to 1.0% by mass.

In the present invention, a surfactant other than the components (b) and (d) may be used, but the content of all the surfactants including the components (b) and (d) is 0.01 to 3. 0.5% by mass,
From the viewpoint of storage stability, it is preferably 0.05 to 2.0% by mass, more preferably 0.05 to 1.0% by mass. As the surfactant that can be used in the present invention,
Surfactants having an alkyl group having 6 to 22 carbon atoms are preferable, and specifically, fatty acid salt, alkane sulfonate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfosuccinate, alkyl Anionic surfactants such as diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkylphenyl ether sulfonate (including amino acid derivatives, etc. Examples thereof include one or more amphoteric surfactants other than the component (d) such as sulfobetaine and nitrogen-type anionic surfactants). However, among the above-mentioned surfactants, anionic surfactants other than the component (d) and fatty acid salts, particularly alkyl sulfonates and alkyl sulfate ester salts, are electrically mixed with the cationic surfactant in the cleaning liquid. Therefore, it is considered that the bleaching effect is lowered because it is considered to act to inhibit the synergistic effect of the hypochlorite ion [(a) component] and the cationic surfactant [(b) component] in the present invention. It was observed. Therefore, for the alkyl sulfonate and the alkyl sulfate ester salt, the cationic surfactant [(b) component] in the composition is used.
The molar ratio of / (alkyl sulfonate and / or alkyl sulfate ester salt) is preferably 0.2 or more,
0.5 or more is more preferable, and 1 or more is particularly preferable.

The composition of the present invention further contains, as the component (e), an alkali metal benzenesulfonate substituted with 1 to 3, preferably 1 with an alkyl group having 1 to 3 carbon atoms, The storage stability at high temperature can be improved. At the same time, the foaming power during spraying can be further improved, and the adhesion to the hard surface during use can be further improved. Among the components (e), as the alkali metal salt,
The sodium salt is preferred. Examples of the component (e) include sodium cumene sulfonate, sodium xylene sulfonate, sodium toluene sulfonate, and the like.
Of these, sodium m-xylene sulfonate is preferable.

The content of the component (e) in the bleaching detergent composition of the present invention is 0.1 to 3.0% by mass,
0.1 to 2.0 mass% is particularly preferable. Within this range, the storage stability of sodium hypochlorite at high temperatures can be increased, and the foaming power during spraying can be further improved.

The liquid bleaching detergent composition of the present invention may contain a perfume ingredient as another optional ingredient. Examples of perfume ingredients that can be added to the hypochlorite system are JP-A-50-74581 and JP-A-62-2.
No. 05200 can be referred to, and single fragrances and mixed fragrances combining them may be used. The fragrance is usually contained in the composition in an amount of 0.001 to 0.5% by mass, but stability may be impaired.

The balance of the composition of the present invention is water, and in view of storage stability, ion-exchanged water or distilled water from which a trace amount of metal ions are removed is preferable. From the viewpoint of storage stability, the content of water is 80 to 98% by mass, more preferably 90 to 98% by mass in the composition.
98 mass% is preferable. Further, it is preferable to adjust the pH of the composition at 20 ° C. to 12.5 to 13.5 from the viewpoint of storage stability and bleaching effect.

The composition of the present invention preferably has a low viscosity in terms of permeability to mold stains and the like, and has a kinematic viscosity of 1 to 1 at 20 ° C. when using an Ostwald viscometer.
0 mm ² / s, it is good to be particularly 1 to 6 mm ² / s.

The liquid bleaching detergent composition of the present invention can be used by directly spraying an object with a sprayer such as a trigger, or by impregnating the composition with a water-absorbing flexible material. A method of rubbing the object and a method of immersing the object in a solution in which the composition is dissolved are preferable, and the method is particularly preferable in terms of simplicity. As a sprayer, there is a trigger type spray capable of spraying a liquid bleaching detergent composition containing components (a) to (c) and water and optionally components (d) and (e) in the form of foam. Preferably, 5 to 1 m ^{2 of} the object
It is preferable to spray at a rate of 15 g.

[0027]

EXAMPLES Example 1 Liquid bleaching detergent compositions shown in Tables 1 and 2 were prepared.
The mass% in the table is the concentration of each component in the composition.
Both compositions have a pH (20 ° C.) of 12.5 to 13.5,
The kinematic viscosity (20 ° C.) was in the range of 1-10 mm ² / s. As the sodium hypochlorite, a 13 mass% aqueous solution was used. With respect to these compositions, the bleaching property (evaluation of the bleaching removing effect of mold stains generated on the resin part) and the ABS resin damage property were evaluated by the following methods. The results are shown in Tables 1 and 2.

<Evaluation of bleaching property> Mold is generated in the soft polyvinyl chloride resin packing used for the bathroom doors of general households under actual use conditions, and a test piece is sampled and cut into about 1 cm to be an evaluation sample. And 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.). The evaluation was carried out using only test pieces having L values within ± 2. Evaluation was performed by stacking two Kimwipe Clark Kimwipes cut into 3 cm × 3 cm on the test piece, dropping 500 μl of the composition, compressing for 15 minutes, then rinsing with water, air-drying, visually observing and evaluating according to the following criteria. did. A: There is no black dullness. B: Almost black dullness is gone. C: Black dullness remains. D: A lump of dirt that is apparently moldy remains.

<Evaluation of ABS resin damage> 230 × 35
Prepare 3 x 2mm ABS resin (manufactured by Mitsubishi Monsanto) test pieces for each composition, and fix the test pieces according to the surface shape of the vinyl chloride resin pipe with a diameter of 276mm as shown in Fig. 1. , And distortion (strain rate 0.74%) as shown in FIG. 2 was generated. The strain rate is calculated by the following equation: strain rate (%) = (I−L) × 100 /
It was determined from L (the definitions of I and L in the formula are shown in FIG. 2). Next, the test piece that has been thus strained, that is, stressed, is covered with absorbent cotton impregnated with 2.0 g of the liquid detergent composition, and the surface of the compress after being left at room temperature (23 ° C.) for 24 hours. The state was visually observed according to the following criteria, and the total score was used as the evaluation result. 4: No abnormality 3: A crack with a length of about 1 mm is slightly recognized on the surface 2: Clearly a crack is recognized 1: The curvature of the test piece changes or breaks

[0030]

[Table 1]

[0031]

[Table 2]

Example 2 A liquid bleaching composition having the composition shown in Table 3 was prepared, and the mold removing effect and the ABS resin damage to the mold stains generated on the soft polyvinyl chloride resin packing were examined in the same manner. The effect was obtained. In addition, the pH of all compositions
(20 ° C.) was in the range of 12.5 to 13.5, and kinematic viscosity (20 ° C.) was in the range of 1 to 10 mm ² / s.

[0033]

[Table 3]

[Brief description of drawings]

FIG. 1 is a perspective view for explaining a method of a substrate damage test in Examples.

FIG. 2 is a cross-sectional view of an ABS resin test piece for explaining a substrate damage test method in Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsukuda Ikkun, 1334 Minato Minato, Wakayama, Wakayama Prefecture, Kao Corporation (56) References JP-A-57-61099 (JP, A) JP-A-7-82593 (JP) , A) JP 2001-192700 (JP, A) JP 2002-249800 (JP, A) JP 2002-241791 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/00-19/00

Claims (2)

(57) [Claims] 1. (a) 0.5 alkali metal hypochlorite salt
To 5.0 mass%, (b) quaternary ammonium type surfactant 0.01 to 0.5 mass%, (c) alkali metal hydroxide 0.2 to 3.0 mass% , (d) carbon Number 8-16 al
Amine oxide type surfactant having one or more kill groups
0.05 to 3.0 mass% and water, the total surfactant content is 0.01 to 3.5 mass%, and [mass% of (a)] and [(b) Mass%] is 0.5
A liquid bleaching detergent composition (cumene sulfonic acid,
Xylene sulfonic acid, toluene sulfonic acid and these
Those containing at least one selected from alkali metal salts
Excluding) . 2. An alkyl sulfonic acid in (b) and the composition
The molar ratio of the salt and / or the alkyl sulfate ester salt is
(B) / (alkyl sulfonate and / or alkyl sulfur
2. The liquid bleaching detergent composition according to claim 1, wherein the acid ester salt is 1 or more .