JP4942981B2 - Hard surface cleaner - Google Patents

Description

  The present invention relates to a cleaning agent for acidic hard surfaces used for cleaning toilet bowls and bathroom walls.

  In recent years, the purchase of a cleaning agent based not only on the cleaning ability but also on whether or not it is a favorite fragrance has increased, and the ratio has been increasing year by year. In particular, consumers are highly aware of the fragrance of products used in their homes. The favorite scent is required to be maintained from the purchase of the cleaning agent to the end of use. In order to satisfy this requirement, even if a fragrance is simply added and blended in the cleaning liquid, the requirement cannot be satisfied. The reason for this is that there are many compounds having ester groups, aldehyde groups, etc. in fragrances, and if a strong acidic aqueous solution or dispersion containing such fragrances is stored for a long period of time, hydrolysis or oxidation of the fragrance occurs during storage. It is. As a result, the initial quality of the cleaning agent may be impaired, such as a change in the appearance of the cleaning agent, a change in smell, or a precipitate.

  Moreover, when using a cleaning agent, the quality of fragrance becomes important and it is necessary to provide consumers with the scent required for the cleaning agent. A cleaning agent using an organic acid is expected to be able to create many types of fragrances, although its cleaning power is inferior to that of strong acids such as hydrochloric acid. There are various factors in the quality of the scent of a product, but “fresh scent”, “clean scent” and the like are required as scents required for toilets and bathrooms. When cleaning agents having these fragrances are used, environmental odors such as excrement odor, drainage mouth odor, sebum odor and mold odor can be expected during cleaning.

  In addition, if a scent such as “fresh scent” or “clean scent” is felt when using a toilet, etc., both toilet washers and toilet users can get a feeling of “freshly cleaned toilet” An important point for toilet users is that the scent continues after washing.

Cleaning agents adjusted to be acidic with organic acids or the like are suitable for hard surfaces, and many cleaning agents suitable for cleaning hard surfaces such as bathroom tiles and toilet toilets have been proposed. It has been proposed to add a fragrance to these cleaning agents (for example, Patent Documents 1 and 2).
JP2003-183697 JP 2004-75764 A

  However, in Patent Documents 1 and 2, only the stability of the fragrance in the cleaning agent is examined, and the quality of the scent and the scent sustainability in the actual use scene are not examined.

  An object of the present invention is to provide a cleaning agent for an acidic hard surface, which is adjusted to a pH of more than 1 and not more than 3.5 with an organic acid, and has a fragrance in a product that is stable over time.

The present invention is a fragrance composition comprising one or more fragrance compounds selected from the following fragrance compound group (A-1) and one or more fragrance compounds selected from the following fragrance compound group (A-2) (hereinafter referred to as “fragrance composition”). , A perfume composition of the present invention), an organic acid, and water, and a detergent for hard surfaces having a pH at 20 ° C. of more than 1 and not more than 3.5.
[Perfume compound group (A-1)]
2-Methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, γ-undecalactone, cachemelan, galaxolide, coumarin, anisyl acetate, cyclopentadeca Nolide, Decenol, Phenylacetic acid, Hexylcinnamic aldehyde, Heliotropin, Methyl β-naphthylketone, Methylatrate, Lilal, Lilyal, 2,4-Dimethyl-4-phenyltetrahydrofuran, α-damascone, γ-nonalactone, dodecahydro -3a, 6,6,9a-Tetramethylnaphtho [2,1-b] furan [fragrance compound group (A-2)]
2,2,5-trimethyl-5-pentylcyclopentanone, 2,2,5,5-tetramethyl-4-isopropyl-1,3-dioxane, 2,4-dimethyl-3-cyclohexenylcarboxaldehyde, 2 -Methyl-2-pentenoic acid, 3,3,5-trimethylcyclohexyl ethyl ether, cis-3-hexenol, l-menthol, l-menton, n-octanal, pt-butylcyclohexanone, β-dynascone, γ-dodecalactone , Acetoxyamyl tetrahydropyran, acetophenone, allyl amyl glycolate, bornyl isoacetate, ethyl 2-tert-butylcyclohexyl carbonate, camphor, jasmolactone, damacenone, tetrahydrolinalol, phenylethyl alcohol, phenylethyl methyl ether, butyldimethyldihydro pyran, ethyl tricyclo [5.2.1.0 ^{2, 6]} decan-2 Irukarubokishi Over DOO, benzaldehyde, borneol, maltol, methyl amyl ketone, methyl hexyl ketone, methylene tetramethyl cycloheptanone, rose oxide, 2,6-dimethyl heptanol, .gamma.-decalactone, creosol, dihydromyrcenol, tetrahydropyran-time goal

  In the present invention, the hard surface refers to the surface of an object made of a substance having a hard property, which is used for a bathtub, an inner wall, etc. in a bathroom, a toilet, etc. in a bathroom, a sink, an inner wall, etc. in a kitchen. means.

  According to the present invention, it is possible to obtain a cleaning agent having extremely high stability over time of a fragrance in a product. The cleaning agent of the present invention contains an organic acid and exhibits desirable effects in terms of detergency and antifouling properties.

  In the fragrance composition of the present invention, those described in the fragrance compound group (A-1) have high scent sustainability, and those described in the fragrance compound group (A-2) have high diffusibility. By using together the perfume compounds belonging to each group, it is possible to realize a cleaning agent having a high storage stability of the perfume composition and a scent required during washing, and a scent having high diffusibility and durability. .

  Among the fragrance compound group (A-1), 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, γ-un is preferable as the fragrance. Decalactone, cachemelan, galaxolide, coumarin, anisyl acetate, cyclopentadecanolide, decenol, phenylacetic acid, hexylcinnamic aldehyde, heliotropin, methyl β-naphthyl ketone, methyl atrate, lyral, lyial, 2,4-dimethyl -4-phenyltetrahydrofuran and the like.

  In the fragrance compound group (A-2), 2,2,5-trimethyl-5-pentylcyclopentanone, 2,2,5,5-tetramethyl-4-isopropyl-1,3 are preferable as the fragrance. -Dioxane, 2,4-dimethyl-3-cyclohexenylcarboxaldehyde, 2-methyl-2-pentenoic acid, 3,3,5-trimethylcyclohexyl ethyl ether, cis-3-hexenol, l-menthol, l-mentholone, n-octanal, pt-butylcyclohexanone, β-dynascone, γ-dodecalactone, acetoxyamyl tetrahydropyran, acetophenone, allyl amyl glycolate, bornyl isoacetate, ethyl 2-tert-butylcyclohexyl carbonate, camphor, jasmolactone, Damasenone, tetrahydrolinalol, phenylethyl alcohol, phenylethyl methyl ether, butyldimethyl Dihydropyran, Furuteto, benzaldehyde, borneol, maltol, methyl amyl ketone, methyl hexyl ketone, methylene tetramethyl cycloheptanone, rose oxide.

  In the fragrance composition used in the present invention, not only those described in the fragrance compound group (A-1) and those described in the fragrance compound group (A-2), but also the intended purpose is achieved. Natural fragrances and essential oils can also be used within the range.

  Further, in combination with the fragrance composition of the present invention, for example, a solvent, specifically, dipropylene glycol, propylene glycol, isopropyl myristate, diethyl phthalate, etc., is appropriately blended within a range not impairing the effects of the present invention. Can do.

  The scent stability is such that the mass ratio of [total mass of fragrance compounds in the fragrance compound group (A-2)] / [total mass of fragrance compounds in the fragrance compound group (A-1)] is 1 or more. And preferred to achieve fragrance diversity.

  The fragrance composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and particularly preferably 0.1 to 0.8% by mass in the cleaning agent in order to achieve the desired fragrance effect of the present invention. % Content.

  The cleaning agent of the present invention preferably contains at least one fragrance compound occupying 30% by mass or more in the total of fragrance compounds selected from the fragrance compound group (A-2).

  The total content of the fragrance compounds in the fragrance compound group (A-1) in the fragrance composition is 20% by mass or more, and the total content of the fragrance compounds in the fragrance compound group (A-2) is 30% by mass or more. It is preferable to achieve the desired scent effect of the present invention.

[Organic acid]
The cleaning agent of the present invention contains water and an organic acid and is adjusted so that the pH at 20 ° C. exceeds 1 and is 3.5 or less, preferably 1.5 to 3.5, more preferably 2 to 3. It is preferable to use at least one of citric acid, oxalic acid, malonic acid, malic acid, tartaric acid, maleic acid, succinic acid, lactic acid and gluconic acid as the organic acid, but citric acid is particularly preferable from the viewpoint of detergency. The organic acid is preferably contained in the cleaning agent in an amount of 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 2.5 to 15% by mass, from the viewpoint of the cleaning property and low-temperature stability of the cleaning agent. . In this case, if necessary, an inorganic acid such as phosphoric acid or sulfuric acid may be used in combination.

[Polymer having amino group and / or quaternary ammonium group]
The cleaning agent of the present invention has 10 to 100 mol% of monomer units [monomer unit (a)] having at least one group selected from an amino group and a quaternary ammonium group in the molecule. And a polymer having a weight average molecular weight of 1,000 to 100,000 (hereinafter referred to as the polymer of the present invention) is preferably contained. In particular, the monomer unit has a monomer unit (a) having at least one group selected from an amino group and a quaternary ammonium group, and a monomer unit (b) represented by —SO ₂ —. (A) is a polymer containing 10 to 99 mol% of all monomer units and having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1 (hereinafter referred to as polymer A of the present invention). It is preferable to contain anti-fouling property.

  In the polymer A, the molar ratio of the monomer unit (b) / monomer unit (a) is preferably 0.01 to 1, more preferably 0.02 to 0.75, and particularly preferably 0.03 to 0.5.

  In the polymer or polymer A of the present invention, the monomer used for constituting the monomer unit (a) includes at least one selected from the compound represented by the following general formula (1) and the compound represented by the general formula (2). Is preferred.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom, a C1-C3 alkyl group, or a hydroxyalkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

In this case, as an anion of Z ⁻ , for example, a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, and an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms And hydroxy ions.

  Specifically preferred as the compound of the general formula (1) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, acryloyl. (Or methacryloyl) oxyalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, N- (ω-alkenyl (C2-10))-N , N, N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, N, N-di (ω-alkenyl (carbon number 2 to 10))-N, N-dialkyl (carbon number 1 to 3) 4 A quaternary ammonium salt is preferred, and diallyldimethylammonium salt is particularly preferred.

  Particularly preferred as the compound of the general formula (2) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N-dialkyl (C1-3) amine, acryloyl (or methacryloyl) oxyalkyl. (C1-5) -N, N-dialkyl (C1-3) amine, N- (ω-alkenyl (C2-10))-N, N-dialkyl (C1-3) amine N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine and diallylamine are preferable, and allylamine and diallylmethylamine are particularly preferable. , Diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, acryloyl (or methacryloyl) oxy Ethyl-N, N-dimethylamine is good. The monomer unit A is contained in a proportion of 10 to 99 mol% with respect to the total monomer units. Preferably it is contained in a proportion of 20 to 99 mol%, more preferably 30 to 90 mol%.

In the polymer A of the present invention, the monomer unit (b) is —SO ₂ —, and as a method for introducing such a monomer unit into the polymer, a predetermined amount of SO ₂ gas is added to the compound of the general formula (1) and And / or blown into a solution containing the compound of general formula (2), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, 2, 2, Polymerization initiator selected from '-azobis (2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfate, and hydrogen peroxide It can be obtained by polymerization using A solvent can be used at the time of polymerization. Specifically, alcohols selected from water, methanol, ethanol and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazo Lydinone, acetonitrile, propionitrile, toluene, xylene and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably -20 to 20 ° C, preferably -10 to 100 ° C. In the present invention, the polymerization can be carried out by light or radiation, and the polymerization can be efficiently carried out by irradiating light having a wavelength of 300 to 450 nm.

  By adding the monomer unit (b), in addition to the rust-preventing effect, even when the concentration of the polymer is low, sufficient adhesion to a hard surface is exhibited, and it is difficult to be affected by the combined use with a cationic surfactant.

  In the present invention, for the purpose of further improving the antifouling effect, the polymer or polymer A of the present invention further contains a monomer unit (c) derived from a monomer selected from the following (i) to (ii). Is preferred.

  (I) Acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonic acid Salt, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (1 to 12 carbon atoms)

  (Ii) Acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N , N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound

  Among these, the monomer unit derived from the monomer (i) is particularly preferable from the viewpoint of the antifouling effect, and among these, acrylic acid or its sodium salt or potassium salt, methacrylic acid or its sodium salt or potassium salt, maleic acid or its sodium Salts or potassium salts are preferred. Here, the counter ion of the monomer unit derived from the monomer (i) may be a cationic group portion of the polymer to be contained.

  When the polymer or polymer A of the present invention has a monomer unit (C), the molar ratio of the monomer unit (C) / monomer unit (A) is 0.05 to 2, more preferably 0.1 to 0.1 from the viewpoint of the antifouling effect. 1, especially 0.2 to 0.5 is preferable.

  The polymer or polymer A of the present invention has a weight average molecular weight of preferably 1,000 to 6,000,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 100,000, particularly preferably 5,000 to 60,000, and this weight average molecular weight is acetonitrile. And a mixed solvent of water and water (phosphate buffer solution) as a developing solvent, and polyethylene glycol as a standard substance by gel permeation chromatography.

  In the present polymer or polymer A, the monomer unit (b), the monomer unit (b), and preferably the monomer unit (c) may be present in either the main chain or the side chain in the polymer. Absent. These may be randomly polymerized, block polymerized, or graft polymerized. In the present invention, it is most preferable to use a polymer composed only of the monomer unit (a), the monomer unit (b), and the monomer unit (c).

  From the viewpoint of achieving the desired antifouling property, the polymer or polymer A of the present invention is preferably contained in the cleaning agent in an amount of 0.02 to 5% by mass, more preferably 0.05 to 2% by mass.

[Surfactant]
In the cleaning agent of the present invention, a surfactant can be used as a detergency enhancing agent. Surfactants include cationic surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants, but those that act synergistically as a detergency enhancer for organic acids include nonionic surfactants. Agents are preferred. From the viewpoint of detergency and stability at low temperature, the surfactant is preferably used in the detergent in an amount of 0.5 to 15% by mass, more preferably 1 to 10% by mass.

<Nonionic surfactant>
The nonionic surfactant used in the present invention is not particularly limited, but polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers Of alkylene oxide-added alkyl group or alkenyl group-containing nonionic surfactants, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants and alkylglycosides One or two or more selected from among them are preferred. Particularly preferred nonionic surfactants include amine oxides. For example, the alkyl or alkenylamine oxide which has a C1-C24 linear or branched alkyl group or alkenyl group is mentioned. More preferable amine oxides include alkylamine oxides represented by the following general formula (3).

In the general formula (3), R ³⁰ is an alkyl group or alkenyl group having 8 to 24 carbon atoms, and an alkyl group having 12 to 18 carbon atoms is particularly preferable. R ³¹ and R ³² are each an alkyl group having 1 to 3 carbon atoms, and a methyl group having 1 carbon atom is particularly preferable, and those having a = 0 and b = 0 are preferable.

<Anionic surfactant>
Although the anionic surfactant used for this invention is not specifically limited, The following are mentioned.
(1) Alkylbenzene sulfonates having a linear or branched alkyl group, wherein the alkyl group has an average carbon number of 8 to 18.
(2) An anionic surfactant having a polyoxyalkylene group, such as polyoxyalkylene alkyl ether sulfate and polyoxyalkylene alkenyl ether sulfate.
(3) Alkyl or alkenyl sulfate, wherein the alkyl or alkenyl group has an average carbon number of 8 to 20.

<Cationic surfactant>
The cationic surfactant is not particularly limited, but a quaternary ammonium salt is preferable, and among them, one or two selected from cationic surfactants selected from the following general formulas (4) and (5) More than species are preferred.

[In the formula, R ⁴⁰ represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and R ⁴¹ represents a methyl group or a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms. R ⁵⁰ represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and X ⁻ represents a halogen ion or an alkyl sulfate residue.

<Amphoteric surfactant>
Although it does not specifically limit as an amphoteric surfactant, In this invention, 1 type, or 2 or more types chosen from betaines represented by following General formula (6), (7), (8) and (9) Is mentioned.

[In the formula, R ⁶⁰ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and R ⁶¹ and R ⁶² may be the same or different and each may be substituted with a hydroxyl group. Represents an alkyl group, R ⁸⁰ represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, Y represents a hydrogen atom or a hydroxyl group, r 1, s 2 and t 3 represent a number of 1 to 3; , U represents a number of 1 to 5, v represents a number of 1 or more, and w and x represent numbers satisfying 0 ≦ w + x ≦ 4]

In general formula (6), R ⁶⁰ is preferably a saturated alkyl group having 8 to 18 carbon atoms, and more preferably a saturated alkyl group having 10 to 16 carbon atoms in terms of detergency. For the same reason, R ⁶¹ and R ⁶² are each preferably a methyl group, an ethyl group or a hydroxyethyl group, and r is preferably 1.

In the general formula (7), R ⁶⁰ is preferably a saturated alkyl group having 8 to 18 carbon atoms and more preferably a saturated alkyl group having 10 to 16 carbon atoms in terms of detergency. For the same reason, R ⁶¹ and R ⁶² are each preferably a methyl group, an ethyl group or a hydroxyethyl group, and s is preferably 1 and t is preferably 1.

In the amidobetaine type amphoteric surfactants (8) and (9) used in the present invention, a saturated alkyl group having 9 to 15 carbon atoms is preferred from the viewpoint of R ⁸⁰ detergency. For the same reason, R ⁶¹ and R ⁶² are each preferably a methyl, ethyl or hydroxyethyl group, u is 2 or 3, v is 1, w is 1 and x is 1.

  Specific examples thereof include alkylamidopropyl-N, N-dimethylacetic acid betaine, alkylamidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, alkylamidopropyl-N, N-dimethyl-propylsulfobetaine, and the like. In terms of detergency and foaming power, lauric acid amidopropyl-N, N-dimethylacetic acid betaine, myristic acid amidopropyl-N, N-dimethylacetic acid betaine, cocamidoamidopropyl-N, N- Preferred are dimethyl acetate betaine, hydroxysulfobetaine, amidopropyl laurate-N, N-dimethyl-2-hydroxypropyl betaine, and the like.

  In addition to the above components, the hard surface cleaning agent of the present invention further adjusts the pH using an alkali agent such as sodium hydroxide, monoethanolamine, diethanolamine, or an inorganic acid such as hydrochloric acid, if necessary, a thickener, Pigments, colorants, bactericides, preservatives and the like can be added as long as the effects of the present invention are not impaired.

  The cleaning agent for hard surface of the present invention is produced by mixing the above components and adjusted to a predetermined pH. The cleaning agent of the present invention is suitable as a cleaning agent for various stains on various hard surfaces around a house made of tile, ceramic, enamel, reinforced plastic (FRP), stainless steel and the like.

Examples 1-6, Reference Examples 1-6 and Comparative Examples 1-6
The fragrance composition shown in Table 1 was blended to prepare the hard surface cleaning agent shown in Table 2, and the following evaluation was performed. The results are shown in Table 3.

(1) Scent stability 50 g of the hard surface cleaning agent shown in Table 2 is taken in each of two 100 ml glass containers and stored at temperatures of 50 ° C. and 5 ° C. (control). After storage, after 2 weeks and 4 weeks, sensory evaluation was performed by comparing the fragrance quality of the hard object surface cleaning agent stored at 50 ° C. with the hard surface cleaning agent stored at 5 ° C. Specifically, ten panelists performed a sensory evaluation on the change in the scent of the cleaning agent. Sensory evaluation regarding the quality of the fragrance was performed in the following five stages.
1: No change 2: Some change 3: Change 4: Change considerably 5: Change drastically

The average value of 10 panelists was calculated, and the evaluation results were indicated by the following symbols. In terms of fragrance stability, it is desirable that the level is ◎ or ◎.
◎: 1 or more and less than 2 ○: 2 or more and less than 3 Δ: 3 or more and less than 4 ×: 4 or more and 5 or less

(2) Scent quality Regarding the scent quality, it was investigated whether the scent like a cleaning agent, in this case “clean scent” or “refreshing scent”, is consistent with the image of each scent. Furthermore, we investigated how long these fragrances last in the space.

  Specifically, 20 ml of detergent was sprayed on the entire floor in the bathroom (depth 2m x width 2m x height 2m), and 10 panelists specializing in the quality of the scent (same match) and sustainability in the bathroom space It was evaluated with.

(2-1) Consistency of scent quality It was evaluated whether the scent in the bathroom space after spraying the cleaning agent matches each scent image. It can be said that when the number of persons evaluated as “clean fragrance” or “fresh fragrance” is 6 or more and 8 or less, the desired fragrance quality is satisfied, and when 9 or more persons are satisfied, the desirable quality is further satisfied. Of the 10 panelists, the number of persons evaluated as described above is shown in the table with the following symbols.
◎: 9 or more ○: 6 or more and 8 or less △: 3 or more and 5 or less ×: 2 or less In terms of the degree of coincidence of scents, it is desirable that the level is ◎ or ○.

(2-2) Diffusivity and sustainability of fragrance A detergent was sprayed in the bathroom, and changes with time after spraying were evaluated. Evaluate fragrance strength after 5 minutes, 30 minutes, and 60 minutes after spraying, diffusibility of fragrance strength after 5 minutes, persistence of fragrance strength after 30 minutes and 60 minutes As the performance was examined.
1. It smells strong enough 2. Strong smell Smell 4 4. Smell weakly. I don't smell

The average of 10 panelists is shown in the table with the following symbols. In the scent sustainability, it is desirable that the level is ◎ and ○ until 30 minutes, and △ after 60 minutes.
◎: 1 or more and less than 2 ○: 2 or more and less than 3 Δ: 3 or more and less than 4 ×: 4 or more and 5 or less

* 1: Mass ratio of [total mass of fragrance compounds in fragrance compound group (A-2)] / [total mass of fragrance compounds in fragrance compound group (A-1)] * 2: [fragrance compound group (A-2 ) Of the fragrance compound] + [total mass of the fragrance compound of the fragrance compound group (A-1)]

* 3: Copolymer of diallyldimethylammonium chloride and maleic acid (molar ratio 2/1), weight average molecular weight 60,000 * 4: of diallyldimethylammonium chloride, maleic acid and sulfur dioxide (molar ratio 2/1/1) Copolymer, weight average molecular weight 30,000

As shown in Table 3, the cleaning agents of Examples 1 to 6 are excellent in fragrance stability. In addition, in terms of the quality of the scent at the time of washing, high evaluation was also obtained in the items of “cleanliness” and “freshness” which are qualities required as a cleaning agent.

  On the other hand, in Comparative Examples 1 to 6, not the result of satisfactory scent stability, but problems such as scent changes during storage occurred. In addition, the scent after the change was far from “clean” and “fresh”.

Claims (6)

One or more fragrance compounds selected from the following fragrance compound group (A-1) and one or more fragrance compounds selected from the following fragrance compound group (A-2), [fragrance compound group (A-2 Nonionic surfactant selected from fragrance compositions, organic acids, and amine oxides having a mass ratio of 1 or more in total mass of fragrance compounds of)) / [total mass of fragrance compounds of fragrance compound group (A-1)] And a hard surface cleaning agent containing water and having a pH of more than 1 and not more than 3.5 at 20 ° C.
[Perfume compound group (A-1)]
gamma - undecalactone, click Marin, f hexyl cinnamic aldehyde, heliotropin, Li Lal, 2,4-dimethyl-4-phenyl-tetrahydrofuran, de decahydro -3a, 6,6,9a-tetramethyl-naphthaldehyde [2,1 -b] furan [fragrance compound group (A-2)]
2, 4-dimethyl-3-cyclohexenyl carboxaldehyde, l - menthone, full E sulfonyl methyl ether, e Chirutorishikuro [5.2.1.0 ^{2, 6]} decan-2-yl-carboxylate, di- hydro mill Se Nord, tetrahydropyran-time goal   The hard surface cleaning agent according to claim 1, comprising at least one fragrance compound occupying 30% by mass or more of the fragrance compounds selected from the fragrance compound group (A-2).   The hard surface cleaning according to claim 1, wherein the organic acid is at least one selected from citric acid, oxalic acid, malonic acid, malic acid, tartaric acid, maleic acid, succinic acid, lactic acid and gluconic acid. Agent.   The hard surface cleaning agent according to any one of claims 1 to 3, wherein the content of the organic acid exceeds 2.5% by mass in the hard surface cleaning agent.   Furthermore, it has 10 to 100 mol% of monomer units having at least one group selected from an amino group and a quaternary ammonium group in the molecule, and the weight average molecular weight is 1,000 to 100,000. The detergent for hard surfaces in any one of Claims 1-4 containing a polymer. The monomer unit having one or more groups selected from an amino group and a quaternary ammonium group of the polymer is derived from a compound represented by the following general formula (1) and / or a compound represented by the general formula (2). The hard surface cleaning agent according to claim 5.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom, a C1-C3 alkyl group, or a hydroxyalkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group. ]