JP2952561B2 - Bathroom cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for bathrooms which has excellent cleaning performance against scum stains and sebum stains in bathtubs and the like and has good storage stability.

[0002]

2. Description of the Related Art Non-ionic surfactants, anionic surfactants, acidic cleaning agents mainly composed of organic acids and solvents; non-ionic surfactants and anionic surfactants; Neutral detergents combined with surfactants; alkaline detergents mainly composed of nonionic surfactants, anionic surfactants and sequestering agents are widely used.

However, dirt in a bathroom such as a bathtub is different from other residential dirt in that the dirt component is mainly metal soap, particularly a fatty acid calcium salt, to which oils such as proteins, nucleic acids and lipids are bonded. It is. Conventional neutral or alkaline cleaning agents cannot decompose this metal stone canscum, but acidic cleaning agents can decompose metal stone canscum. However, the acidic cleaning agent has problems such as dirt re-adhering after cleaning, making rinsing difficult, damaging a bathtub and the like, and causing rough hands.

[0004] From such a viewpoint, a detergent which is neutral and has an excellent detergency against metal stone scum has been developed. No. 61-283696), and a detergent comprising a combination of a cationic surfactant, a nonionic surfactant and a water-soluble solvent (JP-A-61-283699).
), A detergent comprising a combination of a cationic surfactant, a nonionic surfactant and maleic acid (JP-A-61-283).
No. 700), a bathroom detergent (JP-A-1-221497) comprising a combination of a cationic surfactant, a nonionic surfactant, an aminocarboxylic acid and a solvent.

[0005]

However, even with these cleaning agents, the detergency against metal stone canscum cannot be said to be sufficiently satisfactory. For cleaning a bathtub or the like, a sponge is used to clean the surface to be cleaned. I needed to rub. In addition, there are many sebum stains on the human body in bathroom stains, and there is a demand for an improvement in cleaning power for bathroom cleaners. Further, since the bathroom cleaner is usually in a liquid state, it is desired to have a good storage stability that does not cause precipitation or the like during long-term storage.

Accordingly, an object of the present invention is to provide a bathroom cleaning composition which can easily remove dirt and sebum dirt mainly composed of metal stone canscum in a bathtub or the like and has good storage stability. To provide.

[0007]

Accordingly, the present inventors have studied variously the relationship between the three factors of detergency and storage stability against metal stone scum stain and sebum stain, and the type and amount of surfactant. As a result, when a cationic surfactant and an anionic surfactant having a polyoxyalkylene group are used together in a specific ratio, and when a sequestering agent and a water-soluble solvent are combined with this, the above three conditions are satisfied. They have found that a satisfactory cleaning agent can be obtained, and have completed the present invention.

That is, the present invention provides the following components (a) to
(D): comprising (a) a cationic surfactant, (b) an anionic surfactant having a polyoxyalkylene group, (c) a sequestering agent, and (d) a water-soluble solvent, wherein component (a) And a component (b) in a molar ratio of 3/7 to 7/3.

The cationic surfactant of component (a), when used in combination with a sequestering agent, has the function of decomposing and solubilizing a metal stone scum, and in the present invention, a quaternary ammonium is used. Salt-type cationic surfactants are preferable, and particularly those represented by the following general formula (1) or (2) are preferable.

[0010]

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Wherein R ¹ represents a straight-chain or branched alkyl or alkenyl group having 6 to 11 carbon atoms, and R ² represents a methyl group or a straight-chain or branched alkyl or alkenyl group having 6 to 11 carbon atoms. R ³ represents a group having 6 to 11 carbon atoms
Represents a linear or branched alkyl or alkenyl group of
X represents a halogen atom or an alkyl sulfate residue]

In the general formula (1), the preferable chain length of the linear or branched alkyl or alkenyl group represented by R ¹ or R ² is from 6 to 1 from the viewpoints of detergency, irritation and storage stability.
1, but more preferably 8 to 10, and particularly preferably 8. Further, among R ¹ and R ² , a linear or branched alkyl group is preferable, a linear alkyl group is particularly preferable, and a linear alkyl group having 8 to 10 carbon atoms, particularly octyl group is particularly preferable. Further, among the cationic surfactants of the general formula (1), both R ¹ and R ² have 6 carbon atoms.
Preferred are dialkyldimethyl quaternary ammonium salts which are straight-chain or branched alkyl or alkenyl groups of 1 to 11.

The linear or branched alkyl or alkenyl group represented by R ³ in the general formula (2) has a preferred chain length of 6 to 11, more preferably 8 to 10, and particularly preferably 8 to 10. It is. Further, among the R ³ , a linear or branched alkyl group is preferable, a linear alkyl group is particularly preferable, and a linear alkyl group having 8 carbon atoms is more preferable. The number of carbon atoms of R ¹ to R ³ of these cationic surfactants are not preferred as bathroom cleaners because strong irritating in case of 12 or more.

Among the Xs which represent the counter ion of these cationic surfactants, a halogen atom includes a bromine atom, an iodine atom and a chlorine atom, and the alkylsulfuric acid residue includes methanesulfonic acid and ethanesulfonic acid. And the like, and among them, a halogen atom, particularly a bromine atom or a chlorine atom is preferable. Further, from the viewpoint of easy production and availability, it is preferable to use the component represented by the general formula (2) as the component (a).

The component (a) is preferably incorporated in the composition of the present invention in an amount of from 0.1 to 30% by weight, more preferably from 0.3 to 15% by weight, from the viewpoint of scum washing ability. It is particularly preferable to add 0.5 to 10% by weight.

Examples of the anionic surfactant having a polyoxyalkylene group as the component (b) include polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene. Alkenyl aryl ether sulfate, polyoxyalkylene mono- or di-alkyl ether phosphate, polyoxyalkylene mono- or di-alkenyl ether phosphate, polyoxyalkylene mono- or diphenyl ether phosphate, polyoxyalkylene alkyl ether Carboxylate, polyoxyalkylene alkenyl ether carboxylate, polyoxyalkylene alkyl ether acetate, polyoxyalkylene alkenyl ether acetate, and the like. Among polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl ether acetates and polyoxyalkylene alkenyl ether acetates are especially preferred.

The alkyl or alkenyl group in these anionic surfactants preferably has 4 to 26 carbon atoms, more preferably 8 to 24 carbon atoms. Further, these alkyl or alkenyl groups may be linear or branched. Examples of the polyoxyalkylene group in the anionic surfactant include polyoxyethylene, polyoxypropylene, and polyoxybutylene group, and a polyoxyethylene group and / or a polyoxypropylene group are particularly preferable. Further, the number of moles of the polyoxyalkylene group added is preferably 1 to 20, particularly preferably 1 to 10. Further, as the salt in the anionic surfactant, alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, alkanolamines such as mono-, di- or tri-ethanolamine Salts.

Specific examples of more preferred anionic surfactants include polyoxyethylene (EO = 1 to 10) C
_8-24 alkyl ether sulfate, polyoxyethylene (E
O = 1 to 10) C _8-24 alkyl ether acetate.

The component (b) is preferably contained in the composition of the present invention in an amount of 0.1 to 2 from the viewpoints of detergency against sebum stains and storage stability.
1 to 20% by weight is blended, more preferably 0.3 to 15% by weight, and particularly preferably 0.5 to 10% by weight.

The compounding ratio of the component (a) to the component (b) is 3/7 to 7/3 in terms of molar ratio, but is more preferably 4/6 to 6/4. This ratio is less than 3/7 or 7 /
If it exceeds 3, the detergency for sebum dirt decreases, which is not preferable.

Usually, when a cationic surfactant and an anionic surfactant are used in combination, a complex is formed, so that a precipitate is easily formed and there is a problem in storage stability. However, polyoxyalkylene is used as the anionic surfactant. Use of a compound having a group is advantageous in terms of storage stability because the forming power of the complex is weakened.

As the sequestering agent of the component (c),
There is no particular limitation as long as it has the ability to chelate and block metal ions, and examples thereof include hydroxycarboxylic acids or salts thereof, and aminocarboxylic acids or salts thereof. Specifically, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acids, tripolyphosphoric acid,
Ethylene glycol bis (2-aminoethyl ether)
Tetraacetic acid, citric acid, maleic acid, polyacrylic acid,
Examples include isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid and salts thereof. Of these, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, citric acid and salts thereof are particularly preferred.

Component (c) is preferably incorporated in the composition of the present invention in an amount of from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, and more preferably from 1 to 10% by weight, from the viewpoint of scum washing ability.
It is particularly preferable that the content is 5 to 5% by weight.

Although the water-soluble solvent of the component (d) used in the present invention is not particularly limited, the following general formula (3)
One or more selected from compounds represented by formulas (1) to (5), dihydric alcohols having 4 to 12 carbon atoms and monohydric alcohols having 1 to 5 carbon atoms are preferable.

[0025]

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(Wherein, R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and when both R ⁴ and R ⁵ are hydrogen atoms, except .m is an integer of 0, n is an integer of 0, except when both m and n are 0 .R ⁶
And R ⁷ represent an alkyl group having 1 to 3 carbon atoms. R ⁸ represents an alkyl group having 1 to 3 carbon atoms)

In the water-soluble solvent represented by the general formula (3), when R ⁴ and R ⁵ are alkyl groups, the number of carbon atoms is particularly preferably 1 to 4. In the formula (3), m and n of the average addition mole numbers of ethylene oxide (EO) and propylene oxide (PO) are each 0 to 10; The order is not particularly limited, and may be randomly added.
Specific examples of the compound (3) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 2-3) polyoxypropylene (p = 2-3) glycol dimethyl ether (p
Represents the average number of moles added), polyoxyethylene (p =
3) Glycol phenyl ether, phenyl carbitol, phenyl cellosolve, benzyl carbitol and the like. Of these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, polyoxyethylene (p =
1-4) Glycol phenyl ether is preferred.

The compound represented by the general formula (4) includes 1,3-dimethyl-2-imidazolidinone,
1,3-Diethyl-2-imidazolidinone is exemplified as a suitable compound, and as the compound represented by the general formula (5), 3-methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol and the like are preferable. . Examples of the dihydric alcohol having 4 to 12 carbon atoms include isoprene glycol and 2,2,4-trimethyl-1,3-pentadiol. Further, examples of the monohydric alcohol having 1 to 5 carbon atoms include methanol, ethanol, and isopropyl alcohol. By blending these lower alcohols, the low-temperature stability of the composition is improved.

The water-soluble solvent of the component (d) is preferably contained in the composition of the present invention in an amount of 0.1 to 2 from the viewpoint of the cleaning ability against sebum stains.
-20% by weight, more preferably 1-15% by weight, particularly preferably 5-10% by weight.

The hard surface cleaning composition of the present invention further comprises a nonionic surface active agent as a component (e) for the purpose of further improving the detergency against sebum stains and preventing performance deterioration during long-term storage at high temperatures. It is preferable to add an agent and / or an amphoteric surfactant. The nonionic surfactant used in the present invention is not particularly limited, but includes polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxypropylene alkyl ethers, and polyoxyethylene alkyl ethers. Propylene alkenyl ethers, polyoxybutylene alkyl ethers, polyoxybutylene alkenyl ethers, alkylene oxide-added alkyl or alkenyl group-containing nonionic surfactant mixture, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin mono One or more selected from esters, amine oxides, ethylene oxide condensed surfactants and alkyl glycosides are preferred. More specifically, such nonionic surfactants include the following (1) to (11).

(1) Polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers, wherein the alkyl or alkenyl group has an average carbon number of 10
~ 20, and the number of moles of ethylene oxide added is 1 to 30 mol on average. (2) polyoxyethylene alkylphenyl ethers, wherein the average carbon number of the alkyl group is 6 to 12,
The number of moles of ethylene oxide added is 1 to 25 moles on average.

(3) Polyoxypropylene alkyl ethers or polyoxypropylene alkenyl ethers, wherein the average number of carbon atoms of the alkyl group or alkenyl group is 10 to 20, and the number of moles of propylene oxide added is 1 to 1 on average. 20 moles. (4) Polyoxybutylene alkyl ethers or polyoxybutylene alkenyl ethers, wherein the average number of carbon atoms of the alkyl group or alkenyl group is 10 to 20, and the number of moles of butylene oxide added is 1 to 20 on average.
What is a mole. (5) having an alkyl group or an alkenyl group, ethylene oxide and propylene oxide (molar ratio: 0.1 /
9.9-9.9 / 0.1) or ethylene oxide and butylene oxide (molar ratio: 0.1 / 9.9-9.
9 / 0.1), wherein the average carbon number of the alkyl group or the alkenyl group is 10 to 20, and the number of moles of alkylene oxide added per molecule is an average. 1 to 30 mol. (6) Higher fatty acid alkanolamides represented by the following general formula or alkylene oxide adducts thereof.

[0033]

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Wherein R ⁹ is an alkyl or alkenyl group having 10 to 20 carbon atoms, R ¹⁰ and R ¹¹ are the same or different and are H or CH ₃ , p is an integer of 1 to 3, q Is 0
-3. (7) Sucrose fatty acid esters having a fatty acid moiety having an average carbon number of 10 to 20. (8) Fatty acid glycerin monoesters having an average carbon number of the fatty acid portion of 10 to 20.

(9) Amine oxides. For example, an alkylamine oxide or alkenylamine oxide having a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms can be used. More preferred amine oxides include alkylamine oxides represented by the following general formula (a).

[0036]

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In the general formula (a), R ¹² is an alkyl group or alkenyl group having 8 to 24 carbon atoms, and particularly preferably an alkyl group having 12 to 18 carbon atoms. R ¹³ , R ¹⁴
Is an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group having 1 carbon atom. (10) A non-ionic surfactant having a trade name of "Pluronic" (Asahi Denka Co., Ltd.) obtained by condensing ethylene oxide. (11) Alkyl polysaccharides. For example, an alkyl polysaccharide represented by the following general formula: R ¹⁵ (OR ¹⁶ ) _x G _{y wherein} R ¹⁵ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms A phenyl group; R ¹⁶ represents an alkylene group having 2 to 4 carbon atoms;
G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x (average value) is 0 to 5, and y (average value) is 1 to 5.
5 The alkyl glycoside represented by the above formula will be further described. In the formula, x has an average value of 0 to 5. By changing this value, the water content of the cleaning composition for hard surfaces used in the present invention is changed. And crystallinity can be adjusted. That is, the larger the value of x, the higher the water solubility and the lower the crystallinity. A preferred value of x is 0 to 2, and particularly preferably 0. On the other hand, when the average value of y is larger than 1, that is, when a sugar chain of two or more saccharides is used as a hydrophilic group, the binding mode of the sugar chain is 1-2, 1-3, 1-.
It is possible to include any mixture having 4, 1-6 linkages, as well as α-, β-pyranoside linkages or furanoside linkages and their combined modes of linkage. The average value of y in the general formula (3) is 1 to 5, preferably 1 to 5.
1.5, and more preferably 1.1 to 1.4. Note that y
Is determined by the proton NMR method. Also,
R ¹⁵ in the formula has 10 to 10 carbon atoms in terms of solubility and detergency.
Fourteen alkyl groups are preferred. R ¹⁶ is preferably an alkylene group having 2 to 3 carbon atoms from the viewpoint of water solubility. Furthermore,
The structure of G is determined by a raw material of monosaccharide or disaccharide or more. As a raw material of G, glucose, fructose, galactose, xylose,
Mannose, lyxose, arabinose, and mixtures thereof, and the like, and in the case of disaccharides or more, maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, merezitose,
And mixtures thereof. Among these, preferred raw materials are glucose and fructose in monosaccharides and 2
Above sugars, maltose and sucrose. Of these, glucose is particularly preferred in terms of availability. Further, a 1 mol adduct of pentaerythritol / isostearyl glycidyl ether, a 1 mol adduct of sorbitol / isostearyl glycidyl ether, mannitol
1 mol adduct of 2-octyldodecyl glycidyl ether, 1 mol adduct of methyl glucoside / isostearyl glycidyl ether, 1 mol adduct of diglycerin / isostearyl glycidyl ether, at least one in one molecule such as phytantriol Non-ionic surfactants having a long-chain branched alkyl or alkenyl group and at least three hydroxyl groups.

[0038] Among these nonionic surfactants,
(1), (6), (9) and (11) are particularly preferred, and alkyl glycosides are more preferred.

The amphoteric surfactant used in the present invention is not particularly restricted but includes alkyl carboxy betaines, alkyl sulfo betaines, alkyl hydroxy sulfo betaines, alkyl amide carboxy betaines, alkyl amide sulfo betaines, alkyl amide hydroxy sulfo betaines, Examples thereof include an alkylamidoamine type betaine and an alkylimidazoline type betaine, and an alkylamidocarboxybetaine and an alkylamidohydroxysulfobetaine are particularly preferable. As these amphoteric surfactants, those in which the average carbon number of the hydrophobic group is a linear or branched alkyl group having 8 to 24 carbon atoms are preferable.

Among the surfactants of component (e), amphoteric surfactants are more preferred for improving the storage stability of the composition of the present invention, and nonionic surfactants are preferred for improving the washing effect on sebum stains. Surfactants are more preferred. Therefore, in the present invention, it is more preferable to use them in combination.

The component (e) is preferably contained in the composition of the present invention in an amount of 0.1 to 2 from the viewpoints of washing ability against sebum stains and storage stability.
It is more preferable that the content is 20 to 20% by weight and 0.5 to 10% by weight.

Further, the composition of the present invention comprises an alkali agent such as alkanolamine (0.1 to 15% by weight), a thickener,
Pigments, colorants, fragrances, bactericides, preservatives, water and the like in an amount of 100% by weight of the total composition can be added.

The composition of the present invention is produced by mixing the above components according to a conventional method, and the pH is preferably 3 to
12, more preferably in the range of 5 to 10, particularly preferably in the range of 6 to 8. Outside of this range, problems such as rough hands may occur.

The composition of the present invention is suitable for cleaning bathtubs and bathtubs made of tiles, ceramics, enamels, reinforced plastics (FRP), stainless steel, wood, etc., that is, as cleaning agents for bathrooms.

The cleaning method using the composition of the present invention is, as generally performed in the past, after impregnating the composition with a sponge or the like and scrubbing the surface to be cleaned in a bathroom or a bathtub, or Spray on the surface to be cleaned, leave it for a while, then rinse with water. When washing the inside of the bathtub, the composition of the present invention may be added to the residual water after bathing, left for a certain period of time, preferably one hour or more, and then drained. Then, if necessary, the bathtub surface may be rinsed with water. In this case, the composition of the present invention is used in an amount of 0.5 to 100 ppm, preferably 10 to 80 ppm in terms of the concentration of the cationic surfactant.

[0046]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

Examples 1 to 27 and Comparative Examples 1 to 3 Bathroom cleaning compositions having the compositions shown in Tables 1, 2 and 3 were prepared, and their soil removing power and storage stability were evaluated. The results are shown in Tables 1, 2 and 3. The numbers in the table indicate% by weight.

(Evaluation Method of Metal Stone Kenscum Soil Removal Ability and Sebum Soil Removal Ability) Evaluation of these removal powers was carried out by using a polypropylene flooke and a flow chair having a bath stain which does not fall off to the degree of rubbing. Was adhered for several seconds, then lightly rubbed, and the stain removal state was visually evaluated according to the following five levels, and the average value of n = 5 was taken as the evaluation point.

5: Very good stain removal. 4: Good dirt removal. 3: There is unevenness in dirt removal. 2: Degree of dirt being slightly removed. 1: Almost no dirt is removed.

(Effect of removing sebum dirt) Five adults were bathed in a stainless steel bathtub, allowed to stand overnight, then drained, and naturally dried bathtub dirt was used for evaluation. The stain in the bath tub was sprayed with a commercially available sprayer, lightly rubbed with a sponge, rinsed with water, and the state of stain removal was visually judged.

5: Very good stain removal. 4: Good dirt removal. 3: There is unevenness in dirt removal. 2: Degree of dirt being slightly removed. 1: Almost no dirt is removed.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

As shown in Tables 2 to 4, the cleaning composition of the present invention
It can be seen that it has excellent detergency as compared with the case where an anionic surfactant having no polyoxyalkylene group is blended. In addition, when the cleaning composition of the present invention was used, the material to be cleaned was not damaged, and there was almost no irritation to the skin.

[0057]

The cleaning composition of the present invention is excellent in the ability to decompose and solubilize metal stone scum and sebum, so that dirt in a bathroom such as a bathtub can be quickly and easily cleaned. Good long-term storage stability.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI C11D 1:29 1:06 1:68 3:20 3:33 3:43 3:32) (56) References JP-A-56 -12000 (JP, A) JP-A-6-330087 (JP, A) JP-A-61-283697 (JP, A) JP-A-5-311196 (JP, A) (58) Fields investigated (Int. . ^6, DB name) C11D 1/06 - 1/835 C11D 3/20 - 3/43 WPI / L (QUESTEL)

Claims (4)

(57) [Claims] 1. The following components (a) to (d): (a) a cationic surfactant, (b) an anionic surfactant having a polyoxyalkylene group, (c) a sequestering agent, (d) A) a detergent composition containing a water-soluble solvent, wherein the molar ratio of the component (a) to the component (b) is 3/7 to 7/3; 2. The composition according to claim 1, further comprising (e) a nonionic surfactant and / or an amphoteric surfactant. 3. Component (a) is a quaternary ammonium type cationic surfactant, and component (b) is polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl ether carboxylic acid. 3. The composition according to claim 1, which is a salt or a polyoxyalkylene alkenyl ether carboxylate. 4. The composition according to claim 2, wherein the nonionic surfactant is an alkyl glycoside.