JP4130387B2 - Toilet cleaner - Google Patents

Description

  The present invention relates to a toilet cleaning agent containing a quaternary ammonium compound and / or a specific polymer compound and an acid dye, and in particular, flushing by a method such as installing in a tank top of a flush toilet or putting it in a flush toilet tank. The present invention relates to a toilet cleaning agent (hereinafter sometimes referred to as a stationary toilet cleaning agent) that is automatically introduced into the toilet every time.

  A technique of applying a quaternary ammonium compound to a toilet cleaning agent installed in a water storage tank of a flush toilet is known for the purpose of imparting an antibacterial action and an antifouling effect. Patent Document 1 discloses a toilet water treatment agent using a dialkyldimethylammonium halogen salt. Patent Document 2 discloses an antifouling detergent composition for toilets in which an anionic surfactant and a quaternary ammonium compound are used in combination. Patent Documents 3 to 5 disclose techniques of a quaternary ammonium type surfactant and a polymer having a tertiary amino group or a quaternary ammonium group.

  On the other hand, it is also known to use a dye from a aesthetic point of view for a water tank stationary toilet cleaner. Patent Document 6 discloses a fragrance cleaning composition for flush toilets containing a colorant, and in the detailed description of the publication, blue dyes such as Blue No. 1, Blue No. 2, and Blue No. 202 are exemplified. ing. Patent Document 7 discloses a technique for a vehicle toilet sewage treatment deodorant containing a dye for food additives such as Blue No. 1, a dye selected from a triphenylmethane dye and an oxazine dye. Further, as dyes that can be used for toilet cleaning agents or deodorant fragrances, those described in the detailed description of the inventions of Patent Documents 8 to 11 are known.

However, the storage tank stationary toilet cleaner containing these dyes is generally in solid form, and the liquid type contains, for example, the dye in the detailed description of the invention of Patent Document 12. A composition is described.
JP-A-9-141271 JP-A-9-169995 Japanese Patent Laid-Open No. 2002-60786 JP 2002-146397 A Japanese Patent Laid-Open No. 2002-60784 JP-A-6-330096 JP-A-5-138153 JP-A-8-104898 JP-A-8-81695 JP 2000-144177 A JP-A-10-140198 JP-A-4-345699

  The inventors of the present invention have intensively studied a toilet cleaning agent using a quaternary ammonium compound and an acid dye for the purpose of imparting an antibacterial action and an antifouling effect. In such a combined system, in a liquid composition, It has been found that there is a serious problem that storage stability is significantly reduced at low and high temperatures. This is a problem peculiar to liquid type cleaning agents.

  It is an object of the present invention to improve the low-temperature and high-temperature stability of a toilet cleaner containing a quaternary ammonium compound and a dye that can be used in a storage tank stationary type.

In the present invention, the following (a) [hereinafter referred to as component (a)] is 1 to 30% by mass, (b) [hereinafter referred to as component (b)] is 0.001 to 5% by mass, and (c) [hereinafter referred to as component (a)]. , (C) component] is 5-30% by mass, (d) (hereinafter referred to as component (d) is) 0.1-5% by mass, and water, and (c) / (d) = The present invention relates to a toilet cleaner having a mass ratio of 1 to 100, [(a) + (b)] / [(c) + (d)] = 0.1-10.
(A) One type selected from a cationic surfactant (a1) and a polymer compound (a2) containing 10 to 100 mol% of a monomer unit having a tertiary amino group and / or a quaternary ammonium group in the molecule Compound (b) Acid dye (c) Ethylene glycol (d) Water-soluble organic solvent having 3 to 11 carbon atoms and having at least one hydroxy group in the molecule

  ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning agent for toilets which is excellent in stability at low temperature and high temperature and can be used with a storage tank stationary type is obtained.

<(A) component>
Component (a) of the present invention comprises 10 to 100 moles of cationic surfactant (a1) [hereinafter referred to as component (a1)] and a monomer unit having a tertiary amino group and / or a quaternary ammonium group in the molecule. % Of the polymer compound (a2) [hereinafter referred to as component (a2)].

  Examples of the component (a1) include compounds represented by the following general formulas (1) to (3).

[Wherein, R ^1a and R ^2a are each an alkyl group or alkenyl group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, preferably an alkyl group, and R ^1c and R ^1d are each an alkyl group having 1 to 3 carbon atoms. An alkyl group or a hydroxyalkyl group. A is -COO-, OCO-, -CONH-, -NHCO-,

It is. a is a number of 0 or 1. R ^1b is an alkylene group having 1 to 6 carbon atoms, or — (O—R ^1f ) _b —. Here, R ^1f is an ethylene group or a propylene group, preferably an ethylene group, and b is a number of 1 to 10, preferably 1 to 5. R ^1e is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. R ^3a , R ^3b , R ^3c , and R ^3d are two or more (preferably two) of these alkyl groups having 8 to 12 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms or hydroxy groups. It is an alkyl group. X ^- is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]

  The component (a1) can enhance the antifouling effect when used in combination with (a2) described later, but in the present invention, the component (a1) that has bactericidal properties is the component (a1) alone. Use is also effective.

  As the most preferred component (a1) of the present invention, the following may be mentioned.

  The component (a2) of the present invention is a polymer compound containing 10 to 100 mol% of a monomer unit having a quaternary ammonium group and / or a tertiary amino group (hereinafter referred to as monomer unit A). The weight average molecular weight is preferably 1,000 to 6,000,000, more preferably 2,000 to 2,000,000, and particularly preferably 5,000 to 2,000,000. The molecular weight can be measured by gel permeation chromatography using polyethylene glycol as a standard substance.

  Monomer unit A is a monomer that polymerizes a monomer (hereinafter referred to as monomer A) containing a quaternary ammonium group (may be plural) or contains a tertiary amino group (may be plural). A monomer unit obtained by polymerizing (hereinafter referred to as monomer A ′) may be used, or a tertiary amino group may be quaternized by conversion to quaternary ammonium.

  Preferable examples of the monomer A having a quaternary ammonium group include compounds represented by the following general formula (4).

[In formula, R ^{<4a >} , R ^{< 4b>} , R ^<4c> is respectively independently a hydrogen atom, a hydroxyl group, or a C1-C3 alkyl group. B is an alkylene group having 1 to 12 carbon ^{atoms, -COOR 4g -, - CONHR 4g} -, - OCOR 4g -, - R 4h -OCO-R 4g - a group selected from. Here, R ^4g and R ^4h are each independently an alkylene group having 1 to 5 carbon atoms. R ^4d is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or (R ^4a ) (R ^4b ) C═C (R ^4c ) —B—. R ^4e is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^4f 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 ^4f is an alkyl group, a hydroxyalkyl group or a benzyl group, X ⁻ represents an anion. Further, when R ^4f contains a carboxyl group, a sulfonic acid group, or a sulfate group, X ⁻ does not exist, and these groups in R ^4f become anions. Examples of the anion of X ⁻ include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. be able to. ]

  Among these, acryloyl (or methacryloyl) aminoalkyl (C1 to C5) -N, N, N-trialkyl (C1 to C3) quaternary ammonium salt, acryloyl (or methacryloyl) oxyalkyl (C1 to C1) 5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, N- (ω-alkenyl (C3-10))-N, N, N-trialkyl (C1) -3) Quaternary ammonium salt, N, N-di (ω-alkenyl (3 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt is preferred, especially diallyldimethylammonium salt Is good.

  Preferable examples of the monomer A ′ having a tertiary amino group include compounds represented by the following general formula (5).

  Among these, N, N-dialkyl (C1-3) aminoalkyl (C1-5) acrylate (or methacrylate), N, N-dialkyl (C1-3) aminoalkyl (C1-5) ) Acrylamide, N, N-di (ω-alkenyl (3 to 10 carbon atoms))-N-methylamine are preferred, and diallylmethylamine is particularly preferred.

  In the case of quaternizing the monomer A ′, methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate, diethyl sulfate, monochloroacetic acid or a salt thereof, chlorosulfonic acid or a salt thereof, 3-chloro-2- It is preferable to carry out using hydroxypropanesulfonic acid or a salt thereof, ethylene oxide, propylene oxide, or glycidyl ether. In addition, when using ethylene oxide, propylene oxide, and glycidyl ether, it is preferable to make it react, after neutralizing a monomer unit previously with a sulfuric acid, hydrochloric acid, a C1-C12 carboxylic acid, allylsulfonic acid, etc.

  The component (a2) of the present invention includes not only a polymer composed of monomer unit A (or monomer unit A ′, which may be plural types), but also monomer unit A (or monomer unit A ′, plural types). And a polymer composed of another monomer unit (hereinafter referred to as monomer unit B). In this case, the arrangement pattern of the monomer unit A and the monomer unit B (may be plural types) may be any of block, alternating, period, statistics (including random), and graft type.

  A polymer composed of the monomer unit A (and / or the monomer unit A ′) and the monomer unit B can be obtained, for example, by copolymerizing respective precursor monomers. In this case, the monomer unit B is preferably a monomer unit derived from a monomer selected from the following monomer groups (i) to (v), and the monomer unit derived from the monomer described in (i) to (iii) or (v): The monomer unit derived from the monomer (i), (ii) or (v) is most preferable from the viewpoint of the antifouling effect.

(I) Acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, sulfopropyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid or its salt, phosphoric acid Anionic group-containing compound selected from mono-ω-methacryloyloxyalkyl (C 1-12)

(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-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound

(Iii) Acrylic acid (or methacrylic acid) alkyl (1 to 5 carbon atoms), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (1 carbon atom) -5), ester group-containing compound selected from vinyl acetate

(Iv) Ethylene, propylene, N-butylene, isobutylene, N-pentene, isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl -1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, α-methylstyrene, allylamine, N, N-diallylamine, N, N-diallyl-N-alkyl (C 1-5) amine, ethylene oxide , Propylene oxide, 2-vinylpyridine, a compound selected from 4-vinylpyridine

(V) Sulfur dioxide

  In addition to the synthesis method by copolymerization as described above, the polymer having the monomer unit A and the monomer unit B is preferably a monomer containing the monomer unit A in addition to the monomer (i) to (v), particularly preferably the above (i). , (Ii) may be obtained by graft polymerization, or may be obtained by graft polymerization of the monomer of the general formula (4) to the polymer containing the monomers (i) to (v). After the graft polymerization of the monomer of the general formula (5) to the polymer containing the monomers (i) to (v), particularly preferably the polymer containing the monomers (i) and (ii), It may be quaternized.

  The most preferable monomer unit B of the present invention is derived from a monomer having one or more groups selected from a carboxylic acid group and a sulfonic acid group [but not having a quaternary ammonium group], that is, the monomer of the above (i). Monomer unit (hereinafter referred to as monomer unit B ′).

The polymer constituting the component (a2) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and this can be carried out in a bulk, solution, or emulsion system. Radical polymerization may be initiated by heating, but as an initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N-dimethyleneisobutylamidine) Azo initiators such as dihydrochloride, hydrogen peroxide and organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, perbenzoic acid, sodium persulfate, Existing radical initiators such as persulfates such as potassium persulfate and ammonium persulfate, and redox initiators such as hydrogen peroxide-Fe ³⁺ may be used, and in the presence or absence of a photosensitizer. The polymerization may be initiated by light irradiation or radiation irradiation.

  The component (a2) of the present invention may be a single polymer of monomer unit A and a mixture of plural kinds of polymers selected from copolymers of monomer unit A and monomer unit B.

  In the component (a2) of the present invention, a more preferable configuration is that the sum of the monomer unit A (and / or the monomer unit A ′) and the monomer unit B ′ is 50 to 100 mol% with respect to the total monomer units, Most preferably, the molar ratio of monomer unit A (and / or monomer unit A ′), B ′ is such that monomer unit A (and / or monomer unit A ′) / [monomer unit A (and / or monomer unit A ′) + Monomer units B ′] = 0.3 to 0.99, in particular 0.4 to 0.99.

  In the present invention, it is preferable to use the component (a1) and the component (a2) in combination for the purpose of obtaining an excellent antifouling effect. In particular, the component (a1) preferably has a bactericidal property. In that case, the mass ratio of the component (a1) / the component (a2) is preferably 0.1 to 10, more preferably 0.3 to 5, and particularly preferably 0.5 to 2.

<(B) component>
The component (b) of the present invention is an acid dye, and has at least one sulfonic acid group in the molecule, preferably 1 to 5, more preferably from the viewpoint of obtaining a preferable color tone and stability in a toilet cleaner. An acid dye having 1 to 3 is preferable. Specifically, those having a sulfonic acid group are preferable among the dyes selected from the acid dyes described in “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published by Maruzen Co., Ltd.), and the following compounds can be exemplified.

  Specifically, CIAcid Yellow 1, CIAcid Yellow 7, CIAcid Yellow 11, CIAcid Yellow 17, CIAcid Yellow 23, CIAcid Yellow 25, CIAcid Yellow 29, CIAcid Yellow 36, CIAcid Yellow 38, CI Acid Yellow 40, CIAcid Yellow 42, CIAcid Yellow 44, CIAcid Yellow 76, CIAcid Yellow 98, CIAcid Yellow 99, CIFOd Yellow 3, CIAcid Orange 1, CIAcid Orange 7, CIAcid Orange 8, CI Acid Orange 10, CIAcid Orange 10, CIAcid Orange 19, CIAcid Orange 20, CIAcid Orange 24, CIAcid Orange 28, CIAcid Orange 33, CIAcid Orange 41, CIAcid Orange 45, CIAcid Orange 51, CI Acid Orange 56, CIAcid Orange 74, CIAcid Red 1, CIAcid Red 6, CIAcid Red 8, CIAcid Red 9, CIAcid Red 13, CIAcid Red 14, CIAcid Red 18, CIAcid Red 26, CI Acid Red 27, CIAcid Red 32, CIAcid Red 35, CIAcid Red 37, CIAcid Red 42, CIAcid Red 52, CIAcid Red 80, CIAcid Red 82, CIAcid Red 83, CIAcid Red 85, CI Acid Red 88, C. I. Acid Red 89, CIAcid Red 97, CIAcid Red 106, CIAcid Red 111, CIAcid Red 114, CIAcid Red 115, CIAcid Red 133, CIAcid Red 134, CIAcid Red 145, CIAcid Red 154 , CIAcid Red 155, CIAcid Red 158, CIAcid Red 180, CIAcid Red 183, CIAcid Red 184, CIAcid Red 186, CIAcid Red 198, CIAcid Red 249, CIAcid Red 265, CIAcid Red 1 , CIAcid Blue 7, CIAcid Blue 9, CIAcid Blue 15, CIAcid Blue 22, CIAcid Blue 23, CIAcid Blue 25, CIAcid Blue 27, CIAcid Blue 29, CIAcid Blue 40, CIAcid Blue 41 , CIAcid Blue 43, CIAcid Blue 45, CIAcid Blue 59, CIAcid Blue 62, CIAcid Blue 74, CIAcid Blue 78, CIAcid Blue 80, CIAcid Blue 82, CIAcid Blue 83, CIAcid Blue 90 , CIAcid Blue 92, CIAcid Blue 93, CIAcid Blue 100, CIAcid Blue 102, CIAcid Blue 103, CIAcid Blue 104, CIAcid Blue 112, CIAcid Blue 113, CIAcid Blue 117, CIAcid Blue 120 , CIAcid Blue 126, CIAcid Blue 127, CIAcid Blue 138, C.I.Acid Blue 158, C.I.Acid Blue 16

  In the present invention, from the viewpoint of liquid phase stability, CIAcid Yellow 23, CIFOd Yellow 3, CIAcid Red 27, CIAcid Red 18, CIAcid Red 52, CIAcid Red 49, CIAcid Blue 9, CIAcid Blue 112 One or more selected from CIAcid Blue 74 and CIAcid Green 5 are preferred. Among these, C.I.Acid Blue 9, C.I.Acid Blue 112, and C.I.Acid Blue 74 are preferable, and C.I.Acid Blue 112 is particularly preferable in terms of fading.

<(C) component>
The component (c) of the present invention is ethylene glycol.

<(D) component>
The component (d) of the present invention is a water-soluble organic solvent having a total carbon number of 3 to 11, preferably 3 to 8, particularly preferably 3 to 6 and having at least one hydroxy group in the molecule. Compounds of general formula (6) are preferred.

R ^6a − (OR ^6b ) _c − (OR ^6c ) _d (6)
[Wherein R ^6a and R ^6c are a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, c is a number of 1 to 5, preferably 1 to 3, and d is a number of 0 or 1. , R ^6b is an alkylene group having 2 to 5 carbon atoms which may have a hydroxy group. ]

Specific examples of preferred compounds include the following.
Propylene glycol, butylene glycol, hexylene glycol, glycerin, diethylene glycol, dipropylene glycol, diglycerin, triethylene glycol, tripropylene glycol, triglycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl Nyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene Glycol monopropyl ether, dipropylene glycol monobutyl ether, polyoxypropylene (average addition mole number 1 to 3) monomethyl ether, polyoxypropylene (average addition mole number 1 to 3) monoethyl ether, polyoxyethylene (average addition mole number) 1-2) Monophenyl ether, polyoxyethylene (average number of added moles 1-2) Bruno benzyl ether

  In the present invention, in view of storage stability, propylene glycol, butylene glycol, hexylene glycol, glycerin, diethylene glycol, dipropylene glycol, diglycerin, and triethylene glycol are particularly preferable. Propylene glycol, butylene glycol, hexylene glycol, Diethylene glycol and dipropylene glycol are more preferable, and dipropylene glycol is most preferable.

  In the present invention, the water solubility of (d) means that it is dissolved in water in an arbitrary amount at 20 ° C.

<Other ingredients>
In this invention, an effective component can be contained in the cleaning agent for stationary toilets. Specifically, for the purpose of deodorizing and imparting a preferred fragrance, a fragrance (hereinafter referred to as “(e) component”) and a surfactant other than (a) component for the purpose of cleaning effect and storage stability [hereinafter referred to as (f) component It is preferable to contain.

  (E) As a component, a single fragrance | flavor component may be used and it can also be used as a fragrance | flavor composition which contains several fragrance | flavor components by a specific ratio. Perfume ingredients include “Chemicals of Perfume” (Ryoichi Akahoshi, edited by the Chemical Society of Japan, Industrial Chemistry Series, issued on September 16, 1983) and “Synthetic Perfume Chemistry and Product Knowledge” (Genji Into, Chemical Industry Daily) , Issued on March 6, 1996) or "Basic knowledge of perfumes and fragrances" (by Nakajima Motoki, Sangyo Tosho Co., Ltd., issued on June 21, 1995).

  Specific examples include hydrocarbon flavors, alcohol flavors, ether flavors, aldehyde flavors, ketone flavors, ester flavors, lactone flavors, cyclic ketone flavors, and nitrogen-containing flavors.

(A-1): Hydrocarbon-based fragrance α-pinene, β-pinene, camphene, myrcene, limonene, terpineol, terpinolene, osymene, γ-terpinene, α-ferrandylene, p-cymene, β-caryophyllene, β-farnesene 1,3,5-undecatriene, diphenylmethane

(A-2): Alcohol-based perfume trans-2-hexenol, cis-3-hexenol, 3-octanol, 1-octen-3-ol, 2,6-dimethyl-2-heptanol, 9-decenol, 4-methyl -3-decen-5-ol, 10-undecenol, trans-2-cis-6-nonadienol, linalool, geraniol, nerol, citronellol, rosinol, myrsenol, lavandulol, tetrahydrogeraniol, tetrahydrolinalool, hydroxycitronellol, dihydromil Senol, alo-osimenol, terpineol, turpinen-4-ol, l-menthol, borneol, isopulegol, nopol, farnesol, nerolidol, bisabolol, cedrol, patchouli alcohol, vetivero 2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexanol, 4-isopropylcyclohexanemethanol 1- (4-isopropylcyclohexyl) -ethanol, 2,2-dimethyl-3- (3- Methylphenyl) -propanol, pt-butylcyclohexanol, ot-butylcyclohexanol, ambrinol, benzyl alcohol, phenylethyl alcohol, phenoxyethanol, styryl alcohol, anis alcohol, cinnamic alcohol, phenylpropyl alcohol, dimethyl Benzyl carbinol, phenylethylmethylethyl carbinol, 3-methyl-5-phenylpentanol, thymol, carvacrol, orcinol monomethyl ether, eugeno Le, isoeugenol, santalol, isobornyl cyclohexanol, Sandaroa, Bagudanoru, sandal Mai Sol core, Buramanoru, Ebanoru, poly San tall, 2-ethoxy-4-methoxy-methylphenol

(A-3); ether-based fragrance nerol oxide, miloxide, 1,8-cineol, rose oxide, limetolfuran, linalool oxide, butyldimethyldihydropyran, acetoxyamyltetrahydropyran, cedrylmethyl ether, methoxycyclododecane , 1-methyl-1-methoxycyclododecane, ethoxymethylcyclododecyl ether, tricyclodecenyl methyl ether, rubofix, cedroxide, ambroxan, glycalva, boisiris, anisole, dimethylhydroquinone, paracresyl methyl ether, acetanisole , Anethole, dihydroanethole, estragole, diphenyl oxide, methyl eugenol, methyl isoeugenol, benzyl isoeugenol, Phenylethyl isoamyl ether, β-naphthyl methyl ether, β-naphthyl ethyl ether, β-naphthyl isobutyl ether, 2,4-dimethyl-4-phenyltetrahydrofuran, galaxide

(A-4) Aldehyde fragrances Hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, dodecylaldehyde, tridecylaldehyde, trimethylhexylaldehyde, methyloctylacetaldehyde, methylnonylacetaldehyde, trans-2- Hexenal, cis-4-heptenal, 2,6-nonadienol, cis-4-decenal, undecylene aldehyde, trans-2-dodecenal, trimethylundecenal, 2,6,10-trimethyl-5,9-undecadienal , Citral, citronellal, hydroxycitronellal, perilaldehyde, methoxydihydrocitronellal, citronellyloxyacetaldehyde, isocyclocitral , Centenal, Lilal, Bernaldehyde, Dupical, Maceart, Boronal, Setneral, Phenylacetaldehyde, Phenylpropylaldehyde, Cynamic aldehyde, α-Amylcinnamic aldehyde, α-Hexylcinnamic aldehyde, Hydratropic aldehyde, Anisaldehyde, p -Methylphenylacetaldehyde, cuminaldehyde, cyclamenaldehyde, 3- (pt-butylphenyl) -propylaldehyde, p-ethyl-2,2-dimethylhydrocinnamaldehyde, 2-methyl-3- (p-methoxyphenyl) -Propyl aldehyde, pt-butyl-α-methylhydrocinnamic aldehyde, salicylaldehyde, heliotropin, helional, vanillin, ethyl vanillin, Ruvanillin, 10-undecenal, lyial, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 1-methyl-4- (4-methyl-3- Pentenyl) -3-cyclohexene-1-carboxaldehyde, nonanal, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 3,5-dimethyl-3-cyclohexene-1-carboxaldehyde (note that 2,4 -A mixture of dimethyl-3-cyclohexene-1-carboxaldehyde and 3,5-dimethyl-3-cyclohexene-1-carboxaldehyde is commercially available as LIGUSTRAL from QUEST), benzaldehyde, mylacaldehyde

(A-5); ketone-based fragrance acetoin, diacetyl, methyl amyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, methyl heptyl ketone, acetyl diisoamylene, camphor, carvone, menthone, d-pregon, piperiton, Fengchon, geranylacetone, cedryl methyl ketone, nootkatone, α-ionone, β-ionone, methylionone, α-n-methylionone, β-n-methylionone, α-isomethylionone, β-isomethylionone, allylionone , Α-iron, β-iron, γ-iron, α-damascon, β-damascon, δ-damascon, damaserin, α-dynascon, β-dynascon, maltol, ethyl maltol, 2,5-dimethyl-4-hydroxyfuranone , Sugar Lac , P-t-butylcyclohexanone, amylcyclopentanone, heptylcyclopentanone, dihydrojasmon, cis-jasmon, florex, plicatone, 4-cyclohexyl-4-methyl-2-pentanone, p-menten-6-ylpropanone, Acetophenone, p-methylacetophenone, benzylacetone, callone, raspberry ketone, anisylacetone, methylnaphthylketone, benzophenone

(A-6); ester-based fragrance ethyl formate, cis-3-hexenyl formate, linalyl formate, citronellyl formate, geranyl formate, benzyl formate, phenylethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, methyl cyclopentylidene acetate, Hexyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, isononyl acetate, citronellyl acetate, lavandulyl acetate, geranyl acetate, linalyl acetate, mircenyl acetate, tarpinyl acetate, menthin acetate, menthanyl acetate, nopyru acetate, n-acetate Bornyl, isobornyl acetate, pt-butylcyclohexyl acetate, o-t-butylcyclohexyl acetate, tricyclodecenyl acetate, 2,4-dimethyl-3-cyclohexene-1-methanyl acetate, benzyl acetate, phenylethyl acetate, Stylacetate Laryl, cinnamyl acetate, anisyl acetate, paracresyl acetate, heliotropyl acetate, acetyl eugenol, acetylisoeugenol, guayl acetate, cedolyl acetate, vetiberyl acetate, ethyl propionate, isoamyl propionate, citronellyl propionate, geranyl propionate, linalyl propionate, Terpinyl propionate, benzyl propionate, cinnamyl propionate, allyl cyclohexylpropionate, tricyclodecenyl propionate, ethyl butyrate, ethyl 2-methylbutyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, linalyl butyrate, geranyl butyrate, butyric acid Citronellyl, benzyl butyrate, cis-3-hexenyl isobutyrate, citronellyl isobutyrate, geranyl isobutyrate, linalyl isobutyrate, benzyl isobutyrate, isobutyrate Phenylethyl, tricyclodecenyl isobutyrate, ethyl isovalerate, propyl valerate, citronellyl isovalerate, geranyl isovalerate, benzyl isovalerate, cinnamyl isovalerate, phenylethyl isovalerate, ethyl caproate, Allyl caproate, ethyl enanthate, allyl enanthate, ethyl caprate, citronellyl tiglate, methyl benzoate, ethyl benzoate, isobutyl benzoate, isoamyl benzoate, geranyl benzoate, linalyl benzoate, benzyl benzoate, benzoic acid Phenylethyl, methyl phenylacetate, ethyl phenylacetate, isobutyl phenylacetate, isoamyl phenylacetate, geranyl phenylacetate, benzyl phenylacetate, phenylethyl phenylacetate, p-cresyl phenylacetate, methyl cinnamate, ethyl cinnamate Benzyl cinnamate, cinnamyl cinnamate, phenylethyl cinnamate, methyl salicylate, ethyl salicylate, isobutyl salicylate, amyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl jasmonate, dihydrojasmonic acid Methyl, frutate, allyl 2-pentyloxyglycolate, ethyl 3-methyl-3-phenylglycidate, ethyl 2-pentanoate, 4-acetoxy-3-amyltetrahydropyran

(A-7): Lactone fragrance, cyclic ketone fragrance γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, δ-decalactone, coumarin, dihydrocoumarin, jasmonolactone, jasmine lactone, muscone , Civeton, cyclopentadecanone, cyclohexadecenone, cyclopentadecanolide, 12-ketocyclopentadecanolide, cyclohexadecanolide, cyclixadecenolide, 12-oxa-16-hexadecanolide, 11-oxa -16-hexadecanolide, 10-oxa-16-hexadecanolide, ethylan brushate, ethylenedodecanedioate

(A-8): Nitrogen-containing fragrance 6-sec-butylquinoline, 5-methyl-3-heptanone oxime, citronellylnitrile

  The names of the above fragrance ingredients basically followed the description in “Basic knowledge of fragrances and fragrances” (written by Motoki Nakajima, Sangyo Tosho Co., Ltd., issued on June 21, 1995).

  (F) As a component, 1 or more types chosen from anionic surfactant, a nonionic surfactant, and an amphoteric surfactant are suitable.

  Examples of the anionic surfactant include alkyl or alkenyl benzene sulfonate having an alkyl group or alkenyl group having 10 to 18 carbon atoms, and polyoxyalkylene alkyl or alkenyl ether sulfate having an alkyl group or alkenyl group having 10 to 18 carbon atoms. Ester salt, alkyl or alkenyl sulfate ester salt having an alkyl group or alkenyl group having 10 to 18 carbon atoms, α-olefin (10 to 18 carbon atoms) sulfonate, α-sulfo fatty acid salt (10 to 18 carbon atoms), Examples include an anionic surfactant selected from α-sulfo fatty acid (carbon number 10 to 18) lower alkyl (carbon number 1 to 3) ester salt or fatty acid.

Any alkylbenzene sulfonate can be used as long as the average carbon number of the alkyl chain is 10 to 18 among those commonly distributed in the detergent surfactant market. For example, Kao Corporation Neoperex F25 made by Shell, Dobs102 made by Shell, etc. can be used. Industrially, alkylbenzene widely distributed as a detergent raw material can be obtained by sulfonation using an oxidizing agent such as chlorosulfonic acid or sulfurous acid gas. As for the average carbon number of an alkyl group, 10-14 are preferable. In addition, as the polyoxyalkylene alkyl ether sulfate, ethylene oxide (hereinafter referred to as EO) is 1 to a linear or branched primary alcohol or linear secondary alcohol having an average carbon number of 10 to 18, preferably 10 to 16. An average of 0.5 to 5 mol per molecule is added, and this can be obtained by sulfation using, for example, the method described in JP-A-9-137188. The average carbon number of the alkyl group is preferably 10-16. The alkyl sulfate salt is obtained by sulfonating a linear or branched primary alcohol or linear secondary alcohol having 10 to 16 carbon atoms, preferably 10 to 14 with SO ₃ or chlorosulfonic acid, and neutralizing. it can. As the α-olefin sulfonate, a compound having a hydroxy group in a hydrocarbon group, which can be formed by sulfonating an α-alkene having 10 to 18 carbon atoms with SO ₃ and hydrating / neutralizing, A mixture of compounds in which an unsaturated bond is present. In addition, as the α-sulfo fatty acid lower alkyl ester salt, the alkyl group preferably has 10 to 16 carbon atoms, and methyl ester or ethyl ester is preferable from the viewpoint of washing effect. In the present invention, a polyoxyethylene alkyl sulfate salt having 10 to 14 carbon atoms and 1 to 3 EO average addition moles is particularly preferable in terms of skin irritation and cleaning effect. The fatty acid is preferably a saturated fatty acid having 10 to 14 carbon atoms, preferably caprylic acid, capric acid, lauric acid or myristic acid. Fatty acids having an alkyl distribution derived from palm oil or palm kernel oil can also be used. The fatty acid of the present invention is a compound composed only of an alkyl group or alkenyl group and a carboxylic acid group, and does not include compounds such as alkyl ether carboxylic acid and alkylamide carboxylic acid.

  As the salt, sodium salt, potassium salt, magnesium salt, calcium salt, alkanolamine salt, and ammonium salt are preferable, and sodium salt, potassium salt, and magnesium salt are preferable from the viewpoint of cleaning effect.

  As the nonionic surfactant, a compound of the following general formula (7) and / or general formula (8) is preferable.

^R7a- O- ( ^R7bO ) _d- H (7)
[Wherein, R ^7a is an alkyl group or alkenyl group having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and R ^7b is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. d represents an average added mole number of 3 or more and less than 20, preferably 4 or more and 15 or less, particularly preferably 5 or more and 10 or less. ]

R ^8a − (OR ^8b ) _e G _f (8)
[Wherein R ^8a is a linear alkyl group having 8 to 16, preferably 10 to 16, particularly preferably 10 to 14 carbon atoms, and R ^8b is an alkylene group having 2 to 4 carbon atoms, preferably ethylene group or propylene. A group, particularly an ethylene group, G is a residue derived from a reducing sugar, e is an average value of 0-6, f is an average value of 1-10, preferably 1-5, particularly preferably 1-2. Indicates. ]

  Particularly preferable compounds among the compounds of the general formula (7) include the compounds of the following general formula (7-1) and the compounds of the general formula (7-2).

^R7c- O (EO) _g- H (7-1)
[Wherein, R ^7c is a primary linear alkyl group, branched alkyl group or secondary alkyl group having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms. EO is ethylene oxide, and g is 3 or more and less than 20 as an average added mole number. ]

^R7d- O [(EO) _h / (PO) _i ] -H (7-2)
[Wherein, R ^7d is a primary alkyl group having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms. EO represents ethylene oxide and PO represents propylene oxide. h is an average added mole number of 3 to 15, i is an average added mole number of 1 to 5, and the sum of h and i is less than 20. EO and PO may be random addition or EO addition followed by PO addition and vice versa. ]

  In the compound of the general formula (8), G is a residue derived from a reducing sugar, and the starting reducing sugar may be either aldose or ketose, and a triose having 3 to 6 carbon atoms. , Tetrose, pentose, hexose. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, aldose, idose, talose and xylose, and examples of ketose include fructose. In the present invention, among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferred, and glucose is most preferred. As the reducing sugar of G, the above monosaccharide is preferable, but an oligosaccharide obtained by condensing 2 to 5, preferably 2 or 3 of these monosaccharides may be used. Further, a mixture of monosaccharide and oligosaccharide may be used. In this case, the average degree of condensation is 1 to 5, preferably 1 to 3, particularly preferably 1 to 2, and most preferably 1 to 1.5. preferable.

The compound of the general formula (8) can be easily synthesized by subjecting R ^8a — (OR ^8b ) _e —OH and a reducing sugar to an acetalization reaction or a ketalization reaction using an acid catalyst. In the case of an acetalization reaction, these may have a hemiacetal structure or a normal acetal structure.

  As a specific compound of the amphoteric surfactant, a compound of the following general formula (9) and a compound of the following general formula (10) are preferable.

[Wherein, R ^9a is an alkyl or alkenyl group having 8 to 16 carbon atoms, R ^9b is an alkylene group having 1 to 6 carbon atoms, and B is —COO—, —CONH—, —OCO—, — It is a group selected from NHCO-. j is a number of 0 or 1, and R ^9c and R ^9d are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]

[Wherein, R ^10a is an alkyl or alkenyl group having 9 to 23 carbon atoms, and R ^10b is an alkylene group having 1 to 6 carbon atoms. D is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and k is a number of 0 or 1. R ^10c and R ^10d are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ^10e is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. E is a group selected from —SO ₃ ⁻ , —OSO ₃ ⁻ and —COO ⁻ . ]

In the general formula (9), R ^9a is preferably an alkyl group or alkenyl group having 10 to 14 carbon atoms, and particularly preferably a lauryl group (or lauric acid residue) and / or a myristyl group (or myristic acid residue). ). B is preferably —COO— or —CONH—, and most preferably —CONH—. R ^10b preferably has 2 or 3 carbon atoms, and R ^10c and R ^10d are preferably a methyl group.

In the present invention, R ^10a may be a single alkyl (or alkenyl) chain length or a mixed alkyl group (or alkenyl group) having different alkyl (or alkenyl) chain lengths. In the latter case, those having a mixed alkyl (or alkenyl) chain length derived from a vegetable oil selected from coconut oil and palm kernel oil are preferred. Specifically, the cleaning effect is such that the molar ratio of lauryl group (or lauric acid residue) / myristyl group (or myristic acid residue) is 95/5 to 20/80, preferably 90/10 to 30/70. And from the viewpoint of foaming property.

In the general formula (10), R ^10a is preferably an alkyl group having 9 to 15 carbon atoms, particularly 9 to 13 carbon atoms, and R ^10b is preferably an alkylene group having 2 or 3 carbon atoms. D is preferably -CONH-. R ^10c and R ^10d are preferably a methyl group or a hydroxyethyl group. E is -SO ₃ ^-, or -COO ^- are preferred, E is --SO3 ^- is R ^10e in the case of _{-CH 2 CH (OH) CH 2} - are preferred, E is -COO ^- R ^10e in the case of Is preferably a methylene group.

  The component (f) of the present invention is preferably contained from the viewpoint of detergency and foaming power, but an anionic surfactant may reduce the effect of the component (a) and storage stability is lowered. Therefore, it is suitable to refrain from use, preferably 10% by mass or less, particularly preferably 3% by mass or less in the component (f), and the anionic surfactant / (a) component is preferably 1 by mass. Hereinafter, 0.5 or less is particularly preferable.

  As the component (f) of the present invention, the compound of the general formula (8) is most preferable. In particular, the composition containing the fragrance as the component (e) is excellent in solubilization of the fragrance, and has a detergency and a preferable foaming power. The compound of the general formula (8) is preferably 30 to 100% by mass, particularly 50 to 100% by mass in the component (f).

<Toilet cleaning agent>
The component (a) used in the present invention is an important component for the purpose of imparting antifouling properties and antibacterial effects to the toilet cleaner or for the purpose of modifying the toilet surface. The component (b) is a component that is preferably contained from an aesthetic point of view. However, when these components are used in combination, not only the storage stability is affected by the interaction between the component (a) and the component (b), but the effect of the component (a) may be reduced. It has been found that such a phenomenon is likely to occur when the components (a1) and (a2) are used in combination. In the present invention, by containing the component (c) and the specific component (d) in a specific amount and in a specific ratio, the storage stability at both low and high temperatures is improved without reducing the effect of the component (a). be able to.

  The toilet cleaning agent of the present invention contains the component (a) in an amount of 1 to 30% by mass, preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and particularly preferably 7 to 12% by mass. Moreover, (b) component is 0.001-5 mass%, More preferably, it is 0.001-1 mass%, More preferably, it is 0.005-0.5 mass%, Most preferably, it is 0.005-0.1 mass. %contains. From the viewpoint of storage stability, the mass ratio of component (b) / component (a) is preferably 0.0001 to 0.01, more preferably 0.0003 to 0.005, and particularly preferably 0.0005. 0.002.

  Moreover, the toilet cleaning agent of the present invention contains the component (c) in an amount of 5 to 30% by mass, preferably 10 to 30% by mass, more preferably 12 to 30% by mass, and particularly preferably 15 to 25% by mass. Moreover, (d) component is 0.1-5 mass%, Preferably it is 0.3-5 mass%, More preferably, it is 0.5-3 mass%, Most preferably, 0.5-2 mass% is contained. The mass ratio of component (c) / component (d) is 1 to 100, preferably 5 to 50, particularly preferably 8 to 20, and [(a) component + (b) component] / [(c) component + (D) component] has a mass ratio of 0.1 to 10, preferably 0.2 to 5, and particularly preferably 0.3 to 2.

  Although it is optional in the present invention, it is preferable to contain the component (e) for the purpose of preferable aroma and deodorization, and the content thereof is preferably 0.1 to 10% by mass, more preferably 0.5 to 5%. % By mass, particularly preferably 0.5 to 3% by mass. In addition, the component (f) is preferably contained in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 10 to 25% by mass for the purpose of cleaning effect, foamability and storage stability. It is preferable. In addition, when the component (e) is contained, the component (e) / [(a1) component + (c) component + (d) component is used for the purpose of uniformly solubilizing the component (e) in the toilet cleaner. + (F) component] is preferably 0.001-1, more preferably 0.005-0.5, and particularly preferably 0.01-0.2.

  The toilet cleaning agent of the present invention is in the form of a liquid composition in which the above components (a) to (d), optionally (e) and (f) are dissolved or dispersed in water and present in water. It is possible to use ion-exchanged water or distilled water from which a trace amount of metal components are removed, or sterilized water sterilized with hypochlorite or chlorine.

  The pH of the toilet cleaner of the present invention at 20 ° C. is preferably 2 to 12, more preferably 3 to 11, and particularly preferably 5 to 9. As pH adjusters, inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and other organic acids, and the above alkaline agents may be used alone or in combination. In particular, it is preferable to use an acid selected from hydrochloric acid, sulfuric acid, and citric acid and an alkali agent selected from sodium hydroxide, potassium hydroxide, or the above amine compounds. From the viewpoint of ease of use, the toilet cleaner of the present invention has a viscosity at 20 ° C. of 1 to 1000 mPa · s, preferably 1 to 500 mPa · s. Here, the viscosity in the present invention is measured using a B-type viscometer model BM manufactured by TOKIMEC. INC after aging the sample for 30 minutes in a constant temperature bath at 20 ° C.

The toilet cleaning agent of the present invention preferably contains a metal sequestering agent for the purpose of removing calcium-derived deposition components from the toilet surface. As the sequestering agent used in the present invention,
(1) Phosphoric acid compounds such as phytic acid or alkali metal salts or alkanolamine salts thereof (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy- Phosphonic acids such as 1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, and alkalis thereof Metal salts or alkanolamine salts (3) Phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid or alkalis thereof Metal salts or alkanolamine salts (4) Amino acids such as aspartic acid, glutamic acid, glycine or alkali metal salts thereof Alkanolamine salts (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid. Diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine-N, Aminopolyacetic acid such as N-diacetic acid, glutamic acid diacetic acid, ethylenediamine succinic acid or salts thereof, preferably alkali metal salts or alkanolamine salts (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, Organic acids such as lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyltartaric acid or alkali metal salts thereof or alkanolamine salts (7) Aluminoke represented by zeolite A Alkali metal salts or alkanolamine salts of acids (8) Aminopoly (methylenephosphonic acid) or alkali metal salts or alkanolamine salts thereof, or polyethylenepolyamine poly (methylenephosphonic acid) or alkali metal salts or alkanolamine salts .

  Among these, at least one selected from the group consisting of (2), (5), (6) and (7) is preferable, and at least one selected from the group consisting of (5) and (6) above. Species are more preferred. The content is preferably 0.1 to 20% by mass, preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass. These metal sequestering agents are also effective as pH adjusting agents.

  In the present invention, it is preferable to contain a hydrotrope agent for the purpose of improving storage stability. As a particularly preferred compound, benzenesulfonic acid substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms or a salt thereof is used. Can be mentioned. More specifically, preferable examples are p-toluenesulfonic acid, m-xylenesulfonic acid, p-cumenesulfonic acid, and ethylbenzenesulfonic acid. When a salt is used, sodium salt, potassium salt, and magnesium salt are preferable. is there.

  Moreover, you may mix | blend the polyalkylene glycol for the gelation prevention with the washing | cleaning agent for toilets of this invention. Specific examples of the polyalkylene glycol for preventing gelation are preferably polypropylene glycol having a weight average molecular weight of 500 to 20000 and polyethylene glycol determined by gel chromatography using polyethylene glycol as a standard.

  Furthermore, you may mix | blend ethanol with the washing | cleaning agent for toilets of this invention in order to improve the detergency and preservability of a liquid mixture. As a compounding quantity, 0.1-10 mass%, Furthermore 0.2-5 mass%, Especially 0.5-3 mass% is preferable.

  In addition to the above components, the toilet cleaner of the present invention may further contain, if necessary, usual dispersants, preservatives, antioxidants and the like as long as the effects of the present invention are not impaired.

  Prepare the toilet cleaner shown in Table 1, put it in a polypropylene container, seal it with a screwed cap, leave it in a thermostatic bath at 50 ° C. or −10 ° C. for 1 month, and visually check its appearance. Evaluation based on the criteria. The results are shown in Table 1.

(Evaluation criteria)
○: No change in appearance.
Δ: The liquid is cloudy
X: The liquid is separated or precipitated.

(Note) Each component in the table is as follows. The pH was adjusted using a 0.1 N hydrochloric acid aqueous solution and a 0.1 N sodium hydroxide aqueous solution.
-Quaternary ammonium 1: Cocoalkyldimethylbenzylammonium chloride-Polymer 1: Diallyldimethylammonium chloride / maleic acid / sulfur dioxide (molar ratio 65/30/5) copolymer (molecular weight 30,000)
-Dye 1: C.I. I. Acid Blue 112
Solvent 1: Dipropylene glycol Solvent 2: 1,4-butanediol Solvent 3: 1,5-pentanediol Fragrance: β-pinene (20% by mass), citronellol (20% by mass), β-ionone ( 15% by weight), tetrahydrolinalool (25% by weight), limonene (20% by weight),
Surfactant 1: alkyl glucoside (mixture of alkyl groups having 12 and 14 carbon atoms, glucose average condensation degree 1.3 [mixture of condensation degree 1 and 2])

Claims (9)

The following (a) contains 1-30% by mass, (b) 0.001-5% by mass, (c) 5-30% by mass, (d) 0.1-5% by mass, and water. And (c) / (d) = 5-50 , [(a) + (b)] / [(c) + (d)] = 0.1-10.
(A) Polymer compound (a2 ) containing 10 to 100 mol% of a cationic surfactant (a1) and a monomer unit having a tertiary amino group and / or a quaternary ammonium group in the molecule
(B) Acid dye (c) Ethylene glycol (d) Water-soluble organic solvent having 3 to 11 carbon atoms and having at least one hydroxy group in the molecule The toilet cleaner according to claim 1, wherein (a1) is at least one selected from the following compounds.

The toilet cleaner according to claim 1 or 2, wherein (b) is C.I. Acid Blue 112. The toilet cleaner according to any one of claims 1 to 3, wherein (d) is a compound of the following general formula (6).
      R ^6a − (OR ^6b ) _c − (OR ^6c ) _d       (6)
[In the formula, R ^6a , R ^6c Is a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, c is a number of 1 to 5, d is a number of 0 or 1, and R ^6b Is an alkylene group having 2 to 5 carbon atoms which may have a hydroxy group. ] The toilet cleaner according to any one of claims 1 to 4, wherein (d) is a compound selected from dipropylene glycol, 1,4-butanediol and 1,5-pentanediol. Furthermore, (f) 1 type or more surfactant chosen from anionic surfactant, a nonionic surfactant, and an amphoteric surfactant is used for the toilet in any one of Claims 1-5 Washing soap. The toilet cleaner according to claim 6, wherein (f) is a compound represented by the following general formula (8).
      R ^8a − (OR ^8b ) _e G _f                         (8)
[In the formula, R ^8a Is a linear alkyl group having 8 to 16 carbon atoms, R ^8b Is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, e is an average value of 0 to 6, and f is an average value of 1 to 10. ] The toilet cleaner according to any one of claims 1 to 7, wherein the pH at 20 ° C is 5 to 9. The washing | cleaning agent for toilets in any one of Claims 1-8 whose mass ratio of (a1) and (a2) is 0.1-10 by (a1) / (a2).