JP4877917B2 - Cleaning agent in spray container - Google Patents

Description

  The present invention relates to a cleaning agent in a spray container.

  Conventionally, cleaning of bathroom walls and bathtubs has been carried out by attaching a cleaning agent to the object to be cleaned in the form of foam using a trigger sprayer, especially for removing mold containing hypochlorites. In the cleaning agent, the mold removing effect can be improved by adhering it in the form of foam. Moreover, it is preferable to attach a foam having a volume feeling from the point of recalling the cleaning effect.

  On the other hand, adhering and retaining cleaning agents and hypochlorites as active ingredients on the object to be cleaned is required for the purpose of improving the cleaning effect and mold removal effect. As a method for improving adhesion retention, a method for increasing the viscosity of a composition is known. For example, Patent Document 1 discloses a technique of applying a cross-linked polymer compound, and Patent Document 2 discloses. A technique for applying sodium magnesium silicate is disclosed. Patent Document 3 discloses a technique in which a specific surfactant and a hydrophobic organic counter ion are used in combination.

On the other hand, cleaning agents containing polyalkylene glycol disulfate are disclosed in Patent Documents 4 and 5, for example.
JP-A-6-235000 Japanese National Patent Publication No. 11-217596 Japanese Patent Laid-Open No. 11-279591 JP-A-62-89797 JP-A-7-305099

  Although it becomes possible to improve the adherence of the cleaning agent to the object by the techniques of Patent Documents 1 to 3, the foaming property is remarkably impaired when the viscosity is increased. Have difficulty. That is, when a trigger sprayer is used, there is a strong demand for a technique for forming bubbles with high adhesion retention and volume feeling. Further, Patent Document 4 is a technique for preventing gelation of a liquid detergent, and Patent Document 5 is a technique for improving the stability of hypochlorous acid when a specific compound uses a trigger sprayer. There is no specific suggestion of means for improving the adhesion to the surface of the object and providing a volumey foam.

  In the present invention, when the liquid cleaning agent is attached using a trigger sprayer, the cleaning agent tends to flow due to the inclination of the target surface, while on the other hand, when the viscosity is improved in order to improve adhesion. It solves the problem of lowering rumbling. That is, the object of the present invention is to provide a foamed cleaning agent in a spray container that has excellent adhesion and retention on a wall surface and can form a foam with a volume feeling when processed with a trigger sprayer. Is to provide.

  The present invention uses (a) 0.1 to 10% by mass of a surfactant, (b) 0.05 to 3% by mass of polypropylene glycol disulfate or a salt thereof, and a liquid detergent composition containing water as a trigger. The present invention relates to a spray container-containing cleaning agent that is filled in a container equipped with a sprayer.

  The cleaning agent with a spray container of the present invention is excellent in foaming, such as excellent adhesion retention on a wall surface and the like, and capable of forming a foam having a volume feeling.

  The spray container-containing cleaning agent of the present invention is obtained by filling a container having a trigger sprayer with the liquid cleaning composition containing a specific component as described above. Hereinafter, each component contained in the liquid detergent composition will be described in detail.

In the present invention, a surfactant is used as the component (a). Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include alkylbenzene sulfonate having an alkyl group having 10 to 15 carbon atoms, an alkyl sulfate ester salt having 10 to 16 carbon atoms, and an average addition mole of an alkyl group having 10 to 16 carbon atoms and an oxyalkylene group. A polyoxyalkylene alkyl ether sulfate ester salt having 1 to 6 carbon atoms, a polyoxyalkylene alkyl ether methyl carboxylate having an average addition mole number of an alkyl group having 10 to 16 carbon atoms and an oxyalkylene group, 8 carbon atoms Specific examples include -18 fatty acids or salts thereof, alkane sulfonates having 8 to 16 carbon atoms, and olefin sulfonates having 8 to 16 carbon atoms. Examples of the salt include salts of alkali metals such as sodium and potassium, salts of alkaline earth metals such as calcium and magnesium, and salts of amines such as monoethanolamine.

  The nonionic surfactant includes a polyoxyethylene alkyl ether having an average addition mole number of an alkyl group having 10 to 18 carbon atoms and an oxyethylene group having 1 to 12 carbon atoms, 10 to 18 carbon atoms, and an average degree of sugar condensation of 1 ˜2 alkyl glycosides, one or two of the groups bonded to the nitrogen atom is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group, and the remainder is an alkyl group or carbon number having 1 to 3 carbon atoms. Mention may be made of amine oxides which are 1 to 3 hydroxyalkyl groups. Such an amine oxide preferably has one alkyl group having 8 to 18 carbon atoms, more preferably 8 to 16 carbon atoms, and particularly 10 to 16 carbon atoms.

  As the cationic surfactant, one or two of the groups bonded to the nitrogen atom is an alkyl group having 8 to 16 carbon atoms, and the remainder is an alkyl group having 1 to 3 carbon atoms or a group having 1 to 3 carbon atoms. A quaternary ammonium salt which is a hydroxyalkyl group or a benzyl group can be mentioned.

  The amphoteric surfactant includes N, N, N-trialkyl-N-sulfo having one alkyl group having 8 to 18 carbon atoms and two alkyl groups having 1 to 3 carbon atoms which may be interrupted by an amide group. Mention may be made of propylammonium betaine, N, N, N-trialkyl-N- (2-hydroxysulfopropyl) ammonium betaine, N, N, N-trialkyl-N-carboxymethylammonium betaine.

  The liquid detergent composition used for the detergent contained in the spray container of the present invention can be foamed by a trigger sprayer. Accordingly, a surfactant having a foaming property is also selected. In particular, it is preferable to use an anionic surfactant excellent in foaming property as the main surfactant. In addition, as nonionic surfactants, alkyl glycosides are easily foamed and are easily used in combination with other surfactants. Amine oxides and amphoteric surfactants have the property of improving foaming properties, and are preferably used in combination with anionic surfactants.

  Preferable anionic surfactants include polyoxyethylene alkyl ether sulfates, alkyl sulfates and fatty acid salts. In particular, a polyoxyethylene alkyl ether sulfate salt having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of oxyethylene groups of 1 to 6, and an alkyl sulfate ester salt having 10 to 18 carbon atoms And fatty acid salts having 8 to 18 carbon atoms.

  As a preferable surfactant combination, a fatty acid salt having 8 to 18 carbon atoms, more preferably 10 to 14 carbon atoms, particularly 10 to 12 carbon atoms, and an alkyl sulfate ester salt having an alkyl group having 10 to 18 carbon atoms, One or more selected from the group (hereinafter referred to as (a-1)) and one or two of the groups bonded to the nitrogen atom may be bonded with an amidopropyl group, preferably having 8 to 18 carbon atoms, preferably 10 carbon atoms. A combination with an amine oxide (hereinafter referred to as component (a-2)) having a hydrocarbon group of ˜14 and the remainder being an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms is preferable. . The anionic surfactant is preferably an alkali metal salt, an alkaline earth metal salt or an alkanolamine salt, but in consideration of the stability, sodium is particularly useful when used in combination with a bleaching agent such as hypochlorite. Salts or potassium salts are preferred. The surfactant may be blended as a magnesium salt to improve detergency, but the same effect is often obtained even when blended as an inorganic salt such as magnesium sulfate. Viscosity is improved by allowing magnesium ions to coexist in the composition.

  (A-1) and (a-2) are (a-1) component / (a-2) component at a mass ratio of 9/1 to 3/7, particularly from the viewpoint of adhesion retention to the object. The ratio is preferably 8/2 to 4/6, particularly preferably 6/4 to 4/6.

  The spray container-containing cleaning agent of the present invention relates to an invention for improving the adhesiveness and foaming property of foam obtained by treating a liquid cleaning composition filled in a container with a sprayer. Since the combination of the active agent or the surfactant tends to thicken even at a low concentration, there arises a problem that the operation of pulling the trigger becomes heavy. Usually, in order to lower the viscosity, a method such as increasing the blending amount of a water-soluble organic solvent such as ethanol is proposed, but in this case, a large amount of blending is not preferable because the foam adhesion and foaming properties are reduced. . However, in the present invention, by using the component (b), it is possible to improve the foam adhesion and foaming properties and to reduce the viscosity.

  In the present invention, polypropylene glycol disulfate or a salt thereof is used as the component (b). As the preferred component (b), the average molecular weight of the polypropylene glycol moiety is 100 or more and 4000 or less, and further 400 or more and 2000 or less. The average molecular weight was calculated from the hydroxyl value according to the method described in JIS K 0070. Moreover, as a salt, alkali metal salts, such as sodium salt and potassium salt, are preferable.

  Generally, increasing the viscosity of a liquid cleaning agent improves adhesion retention on the target surface. However, it is impossible to form a foam with a volume feeling. Foam with bubbles is formed, but adhesion retention is reduced. The component (b) of the present invention can reduce the viscosity while maintaining the adhesion retention of the liquid cleaning agent that increases the viscosity and improves the adhesion retention. Both sexes can be achieved.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 3 to 20 mPa · s, more preferably 3 to 10 mPa · s, and most preferably 3 to 8 mPa · s. Here, the viscosity was measured using a B-type viscometer (manufactured by TOKIMEC), rotor No. 1. Viscosity after stirring at 60 rpm for 1 minute under the conditions of 1, 20 ° C.

<Liquid cleaning composition>
The liquid detergent composition of the present invention preferably contains 0.1 to 10% by mass, more preferably 0.5 to 5% by mass of component (a). When used as a liquid bleach detergent, 2.0% by mass. It is preferable that: Moreover, it is preferable to contain (b) component 0.05-3.0 mass%, 0.05-2.0 mass%, especially 0.1-1.0 mass%.

  The liquid cleaning composition of the present invention further contains (c) an alkali metal hypochlorite salt (hereinafter referred to as component (c)) and (d) an alkaline agent (hereinafter referred to as component (d)). Is preferred. In particular, when it is used as a liquid bleaching agent or a mold removal cleaning agent, it is preferable to contain these components (c) and (d).

  Examples of the alkali metal hypochlorite of component (c) include sodium hypochlorite and potassium hypochlorite, and it is particularly preferable to contain sodium hypochlorite.

  Moreover, the alkali agent of (d) component is contained in order to make pH of a composition alkaline, and caustic alkali (alkali metal hydroxide), a silicate, etc. are mentioned. Sodium hydroxide, potassium hydroxide and the like are used as the caustic, and sodium silicate is used as the silicate. Of these, sodium hydroxide is preferably used.

  When the liquid detergent composition of the present invention is applied as a mold removing detergent, the component (c) is 0.1 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, particularly 1.0 to 3%. It is preferable to contain 0.0 mass%. (D) Content of a component is measured by the method of ASTM D 2022-89. That is, in this method, the amount of free alkali in the bleaching agent is measured as sodium hydroxide (NaOH). Also in the present invention, the amount of free alkali in the composition obtained by this method is determined in the composition. (D) The amount of component. (D) It is preferable to mix | blend 0.1-1.0 mass% of component, 0.2-0.8 mass%, especially 0.3-0.7 mass%.

In this invention, the foam characteristic at the time of spraying can be improved by using together with the component (b) the compound represented by the following general formula (1) [hereinafter referred to as component (e)].
_{^{X 1 -O (EO) n -X}} 2 (1)
(In the formula, EO represents an ethyleneoxy group, n represents the average number of added moles of an alkyleneoxy group, and is a number from 10 to 100. X ¹ and X ² are —SO ₃ H, —CH ₂ COOH, or these (It is an alkali metal salt or a hydrogen atom.)

  When the component (e) is blended, the mass ratio of the component (b) / the component (e) is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 5, from the viewpoint of foam characteristics. 3.

  The liquid detergent composition of the present invention contains the above components (a) and (b), but when used as a mold removal detergent, the components (c), (d), and (e) are further added. It is preferably in the form of an aqueous solution dissolved in water, and it is preferable to use ion-exchanged water or the like excluding components such as metals present in a trace amount. The water content is preferably 80 to 98% by weight, in particular 90 to 98% by weight.

  Furthermore, the liquid detergent composition of the present invention preferably adjusts the pH at 20 ° C. to 7 to 14, and when applied to the mold removing detergent containing component (c), the pH at 20 ° C. is adjusted to 11 to 11. 14, more preferably 12 to 14, and particularly preferably 12.5 to 13.5.

  In the liquid cleaning composition of the present invention, as other optional components, components that are generally added to the cleaning agent can be added with care so as not to impair the effect on the effect.

  In order to improve foaming power during spraying, cumene sulfonic acid, xylene sulfonic acid, toluene sulfonic acid, or an alkali metal salt thereof can be blended as an optional component. Among these, metaxylenesulfonic acid or a sodium salt thereof is particularly preferable. The content in the composition is preferably from 0.1 to 3% by mass, particularly preferably from 0.2 to 2% by mass.

  For the purpose of improving the detergency of organic dirt and inorganic dirt, a water-soluble solvent and a chelating agent which are generally blended in a detergent can be blended. As the water-soluble solvent, an alcohol having 1 to 4 carbon atoms and a glycol compound having 2 to 10 carbon atoms are preferable. The chelating agent is preferably an organic acid such as citric acid or an amine compound such as ethylenediaminetetraacetic acid or nitrile triacetic acid. The content in the composition is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 7% by mass. When the composition of the present invention is used as a bleaching composition, particularly when hypochlorite is blended, the blending of these compounds is sufficiently studied from the viewpoint of the stability of hypochlorite. Is done.

  When blending a fragrance, a stable fragrance should be selected particularly when used in combination with the alkali metal hypochlorite of component (c). This fragrance may be a single fragrance or a combination fragrance combining them. Usually, the fragrance is contained in the composition in an amount of 0.001 to 0.5% by mass. However, since there is a risk of impairing the stability, care must be taken in determining the blending components and blending amounts.

Incorporation of the inorganic electrolyte (excluding alkali metal hypochlorite) into the aqueous surfactant solution increases the viscosity of the solution. Examples of the inorganic electrolyte include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium chlorate, potassium chlorate, sodium chlorite, potassium chlorite, magnesium sulfate, and magnesium chloride.

<Cleaning agent in spray container>
The spray container-containing cleaning agent of the present invention is obtained by filling the above-described liquid cleaning composition into a container having a trigger sprayer having a foam formation mechanism. As the trigger type sprayer, those described in Japanese Utility Model Publication No. 6-34858 and Japanese Patent Publication No. 63-2668 can be used. In the present invention, in particular, (i) it has a foam formation mechanism, (ii) the discharge area of the discharge port is 0.3 to 0.7 mm ² , and (iii) 0.3 to 2.0 g in one stroke. A trigger sprayer that discharges the liquid bleach composition is preferred.

  As the bubble forming mechanism, a spin element and a liquid passage plate having several baffle plates installed in a circular space having a diameter of 4 to 8 mm are preferable. Here, the spin element is a mechanism that applies a spin to the flow of the liquid substance through the spin element, and finally ejects the liquid from the nozzle. The detailed structure is disclosed in JP-A-8-332422 and JP-A-8-108102. 4 (b), Japanese Patent Application Laid-Open No. 2002-68265, and the like can be referred to.

  The liquid passage plate, which is another member of the foam formation mechanism, is preferably one in which 3 to 8 baffle plates are installed in a circular space portion having a diameter of 5 to 7 mm. In this case, a rectangular baffle preferably having a width of 0.8 to 1.2 mm and a length of 2 to 4 mm is suitable. Further, the area occupied by the baffle plate with respect to the space portion excluding the baffle plate is preferably 30 to 90 area%, preferably 40 to 80 area%, more preferably 40 to 70 area%. By installing, the adhesion and retention of bubbles on the vertical surface is improved.

  The container of the detergent with a spray container used for this invention can use the container generally used. For example, it is obtained using polyethylene as a raw material, and can be produced by blow molding or the like. The wall thickness of the container may be different from the bottom surface and the side surface, and is 0.05 to 2.0 mm. When the component (c) hypochlorite is blended, the container is opaque in order to suppress decomposition by light. A container containing titanium oxide or the like is used for making the container opaque. In this case, the container has a multilayer structure, and the layer in contact with the innermost liquid cleaning composition is preferably made of metal. Those not included are used. The amount of the liquid detergent composition filled in the container is desirably 200 to 700 ml for handling. In addition, the filling of the liquid is performed leaving a common sense gap.

  The spray container-containing cleaning agent of the present invention is attached to a vertical surface or an inclined surface such as a bathroom wall or window glass in the form of foam using the trigger sprayer. By leaving it for 5 to 120 minutes after the adhesion, the component (a) or the component (c) stays in the adhered part and can act on the object to be cleaned for a long time. After adhering, it may be rinsed as it is, or may be rubbed with a water-absorbing flexible material such as sponge.

  Liquid detergent compositions shown in Tables 1 and 2 were prepared, and the viscosity was measured. Thereafter, the liquid detergent composition was filled into a container equipped with a trigger sprayer (using a Kao mold remover highter container and trigger). According to the evaluation method described later, the state of the foam at the time of spraying was evaluated by the foam specific dissolution and the adhesion retention of the foam. The results are shown in Tables 1 and 2. The composition of Table 2 can be used as a chlorine bleach.

<Evaluation of viscosity>
For the compositions in Tables 1 and 2, using a B-type viscometer (manufacturer: TOKIMEC), rotor No. The viscosity was measured under the conditions of 1, 20 ° C., 60 rpm and 60 seconds (unit: mPa · s).

<Measurement of foam specific volume>
Foam volume (mL) when the liquid detergent composition prepared in Tables 1 and 2 is sprayed 10 times into a 200 mL graduated cylinder using mold taker higher trigger (spray amount 1 g / time) manufactured by Kao Corporation Is read. Further, the lower two digits of the spray amount (g) at that time were measured using a balance, and the specific formula of foam (mL / g) = foam volume (mL) / spray amount (g) was calculated. The larger the value, the better the effect and visibility.

<Evaluation of adhesion and retention of foam>
The range of the width 10cm from the place where the liquid detergent composition prepared in Tables 1 and 2 was 10cm away along the tile joint of the bathroom wall on which a 10cm x 10cm earthenware tile was stretched using a trigger sprayer The area from the position where the bubbles adhered to the position where the bubbles dropped after 15 seconds was calculated. However, the part where the bubbles disappear is not counted. In the table, there is little foaming and the adhesion retention property cannot be evaluated (Comparative product 2-1), or the foam disappears quickly and the foam is poor (Comparative product 1-1). Indicated as "-".

・ Fatty acid salt 1: Sodium caprate (98% product)
Fatty hydrochloric acid 2: Sodium salt of Lunac L-70 (a mixture of fatty acids with a composition ratio of capric acid 10, lauric acid 76, myristic acid 14), manufactured by Kao Corporation Myristyl dimethylamine oxide: Farmin DM4098 Myristylamine A sample synthesized from Kao Corporation and hydrogen peroxide (Nippon Peroxide).
Compound 1: Polypropylene glycol 400 (Sanyo Chemical Industries, Ltd., average molecular weight 402) and a disulfate ester type sodium salt synthesized with anhydrous sulfuric acid. Compound 2: Polypropylene glycol 1000 (Sanyo Chemical Industries, Ltd., average molecular weight 984) ) And disulfate-type sodium salt synthesized with anhydrous sulfuric acid: Sodium hypochlorite: Sodium hypochlorite, manufactured by Nankai Chemical Industry Co., Ltd. Sodium hydroxide: 48% liquid caustic soda, Nankai Chemical Industry Co., Ltd. (The numerical values in the table indicate the amount of free sodium hydroxide.)
Compound 3: Polyethylene glycol 1000 (Sanyo Chemical Industries, Ltd., molecular weight 1020) disulfate ester type sodium salt synthesized with sulfuric anhydride

  From Table 1 above, it is suggested that the foam properties can be improved by adding polypropylene glycol sulfate diester to a system containing only fatty acids as a surfactant, and the foaming property at the time of spraying and the persistence and adhesion of the foam can be improved. . Table 2 shows a blending example of a surfactant system in which an amine oxide and a fatty acid salt are mixed as a surfactant. A combination of an amine oxide and a fatty acid salt, or an inorganic electrolyte tends to increase the viscosity of the system, so that the triggering operation tends to be heavy. It can be seen that the compositions disclosed in Table 2 have no effect of thickening and have suitable foam properties. Moreover, the composition of Table 2 is also an example which mix | blends hypochlorite, and is useful as a mold removal agent.

Claims (7)

(A) Surfactant [hereinafter referred to as component (a)] 0.5 to 5 % by mass, (b) Polypropylene glycol disulfate or salt thereof (hereinafter referred to as component (b)) 0.05 to 3% by mass , And a water-containing liquid detergent composition having a viscosity of 3 to 20 mPa · s at 20 ° C. , filled in a container having a trigger sprayer, and containing the liquid in the spray container The cleaning composition comprises (a) component (a-1) a fatty acid salt having 8 to 18 carbon atoms (hereinafter referred to as (a-1) component) and (a-2) a group bonded to a nitrogen atom. 1 or 2 which may be bonded with an amidopropyl group, having a hydrocarbon group having 8 to 18 carbon atoms, and the rest being an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms A certain amine oxide [hereinafter referred to as (a-2) component and A spray container-containing cleaning agent . The cleaning agent in a spray container according to claim 1, wherein the liquid cleaning composition further comprises (c) an alkali metal hypochlorite and (d) an alkali agent. The cleaning agent in a spray container according to claim 1 or 2, wherein the average molecular weight of the polypropylene glycol part of the component (b) polypropylene glycol disulfate is 400 or more and 2000 or less. The detergent with a spray container in any one of Claims 1-3 whose mass ratio of (a-1) component / (a-2) component in a liquid detergent composition is 9 / 1-3 / 7. . (A) The cleaning agent with a spray container of any one of Claims 1-4 which contains a 2.0 mass% or less component, and is used as a liquid bleach cleaning agent. The spray container according to any one of claims 1 to 5, wherein the liquid detergent composition further comprises (e) a compound represented by the following general formula (1) [hereinafter referred to as component (e)]. Entering cleaning agent.
    X ¹ -O (EO) _n -X ²                   (1)
(In the formula, EO represents an ethyleneoxy group, n represents the average number of moles added of an alkyleneoxy group, and is a number from 10 to 100. X ¹ , X ² Is -SO _Three H, -CH ₂ COOH, or an alkali metal salt thereof, or a hydrogen atom. ) The detergent with a spray container of Claim 6 whose mass ratio of (b) component / (e) component in a liquid detergent composition is 1-10.