JPH07233392A - Cleaner composition for hard surface - Google Patents

Abstract

PURPOSE:To obtain the subject composition having a good cleaning property for a scum smudge on a hard surface in a bath room, etc., and weak stimulation property to a skin of hand, constituted by combining a specific amide type of an ammonium salt with a metal ion blocking agent. CONSTITUTION:This composition is constituted by containing (A) a cationic surfactant of formula I [R<1> is a 1-30C alkyl or an alkenyl; R<2> is H or a 1-5C alkyl; R<3> is a 1-30C alkyl, an alkenyl, an aralkyl, an aryl or formula II; (l) and (n) are each 0-3; (p) and (m) are each 0-1 (provided, (l), (m) and (n) are not simultaneously 0); A is formula III; (x) is a halogen or an alkylsulfate group; and (q) is a number of cations], preferably a quaternary ammonium salt of formula IV ((r) is 1-6), etc., (B) a metal ion blocking agent (e.g. ethylenediaminetetraacetic acid, etc.), and preferably further (C) a water soluble solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard surface cleaning composition, and more particularly to a hard surface cleaning composition having good cleaning performance against scum stains on a hard surface such as a bathroom.

[0002]

As a cleaning agent for hard surfaces, especially bathrooms and bathtubs, nonionic surfactants, anionic surfactants,
Acidic detergent mainly composed of organic acid and solvent; Neutral detergent combined with nonionic surfactant and anionic surfactant; Nonionic surfactant, anionic surfactant and sequestering agent Alkaline cleaners mainly composed of are widely used.

However, stains in bathrooms, bathtubs, etc. are different from the stains in other houses, and are mainly composed of metal soap, especially fatty acid calcium salt, to which oils such as proteins, nucleic acids and lipids are bound. Is. Conventional neutral detergents and alkaline detergents cannot decompose this metallic stone Kenscum, but acidic detergents can decompose metallic stone Kenscum. However, the acidic cleaning agent has problems such that dirt is redeposited after cleaning to make it difficult to rinse, damage the bathtub and the like, and cause rough hands.

From this point of view, a detergent which is neutral and has an excellent detergency against metallic stone Kenscum has been developed, and a neutral detergent containing a combination of a cationic surfactant and a nonionic surfactant has been developed. No. 61-283696), a detergent containing a combination of a cationic surfactant, a nonionic surfactant and a water-soluble solvent (JP-A-61-283936).
No.), a cationic surfactant, a nonionic surfactant and maleic acid in combination (JP-A-61-283).
No. 700) has been reported.

[0005]

However, even with these cleaning agents, the detergency against metal stone Kenscum dirt cannot be said to be sufficiently satisfactory, and for cleaning bathrooms, the surface to be cleaned should be cleaned by using a sponge or the like. I had to rub. Therefore, an object of the present invention is to provide a detergent composition which is capable of easily removing a hard surface, particularly stains mainly composed of metal stone Kenscum of a bathroom or the like, and which is not irritating to hand skin.

[0006]

Accordingly, the present inventors have made various studies on the relationship between the detergency against stains formed by metal stone Kenscum and oil and the chemical structure of the cationic surfactant, and as a result, amide type quaternary It was found that, when the ammonium salt was combined with a sequestering agent, excellent detergency was obtained as compared with the case of using other cationic surfactant, and the irritation to the hand skin was weak, and the present invention was completed. Came to do.

That is, the present invention comprises the following components (a) and (b): (a) a cationic surfactant represented by the general formula (1).

[0008]

[Chemical 5]

[In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents A linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, an aralkyl group, an aryl group,

[0010]

[Chemical 6]

## EQU1 ## where l, l ', n and n'represent numbers 0 to 3 respectively, and p, m and m'represent 0 or 1 (provided that l, m and n or l' , M ′ and n ′ cannot be 0 at the same time), A is

[0012]

[Chemical 7]

X represents a halogen atom or an alkylsulfate residue, and q represents the number of cations in the formula (1). (B) A hard surface cleaning composition containing a sequestering agent To do.

The cationic surfactant as the component (a) has an action of decomposing and solubilizing the metal stone Kenscum when used in combination with the sequestering agent. Among the quaternary ammonium salts of the above general formula (1), the following formulas (1a), (1b), (1c), (1d), (1e)
And a compound represented by (1f) are more preferable, a compound represented by formula (1a), (1b) or (1c) is further preferable, and a compound represented by formula (1a) or (1c) is particularly preferable.

[0015]

[Chemical 8]

[Wherein, r and s are numbers 1 to 6, and R
¹ , R ² , R ³ and X are the same as above]

The alkyl or alkenyl group represented by R ^{1 in} the above general formula (1) has 6 to 20 carbon atoms, more preferably 6 to ¹ carbon atoms.
6, especially 8 to 12 are preferable from the viewpoint of detergency. Further, among the alkyl group and the alkenyl group, an alkyl group is preferable, and a linear alkyl group is particularly preferable. More preferred R ¹
Specific examples of include octyl, decyl, lauryl, myristyl, palmityl and stearyl groups.

R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, isobutyl and s.
Examples include ec-butyl, t-butyl, pentyl and the like.
A hydrogen atom is particularly preferable as R ² . Examples of the alkyl group or alkenyl group for R ³ include the same groups as those for R ¹ , but an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group is particularly preferable. Further, examples of the aralkyl group of R ³ include a benzyl group and a phenethyl group, and a benzyl group is particularly preferable. A phenyl group is preferred as the aryl group of R ³ . As l, l ', n and n', 1-3 are preferable, and 1-2 are particularly preferable. Moreover, as r, 1-3 are more preferable, and 2 is especially preferable.

Among Xs which represent the counter ion of these cationic surfactants, examples of halogen atom include bromine atom, iodine atom and chlorine atom, and examples of alkyl sulfuric acid residue include methanesulfonic acid and ethanesulfonic acid. Among these, a halogen atom, especially a bromine atom or a chlorine atom is preferable.

Of the compounds represented by the above (1a) to (1f), the compound (1a) is, for example, JP-A-5-1558.
Compound (1b) to compound (1f) can be produced, for example, according to the following reaction formula by the method described in JP-A-35-35.

[0021]

[Chemical 9]

[In the formula, R ¹ , R ² , R ³ and X are the same as above]

The primary amines or ammonia (2) can be added to 3-
A compound (1b) is obtained by reacting a chloro-2-hydroxypropyl-substituted ammonium salt (3) to obtain a compound (4), and then reacting this with a fatty acid (5), a fatty acid halide, a fatty acid anhydride and the like. To be

[0024]

[Chemical 10]

[Wherein R ¹ , R ² , R ³ , r and X are the same as defined above]

Compound (1c) is obtained by reacting fatty acid (5) with dimethylaminoalkylamine (6) to give compound (7) and then quaternizing.

[0027]

[Chemical 11]

[Wherein R ¹ , R ² , r and X are the same as above]

The primary amine or ammonia (2) is reacted with alkylene dichloride (8) to obtain compound (9), which is reacted with fatty acid (5), fatty acid halide, fatty acid anhydride and the like to form amide (10). ) And then reacting it with dimethylamine to give compound (1
d) is obtained.

[0030]

[Chemical 12]

[Wherein R ¹ , R ² , R ³ , r and X are the same as defined above]

The compound (1c) was replaced with epichlorohydrin (1
Compound (1e) is obtained by reacting 1).

[0033]

[Chemical 13]

[Wherein R ¹ , R ² , R ³ , r, s and X
Is the same as above]

Compound (1f) is obtained by reacting compound (1c) with alkylene dichloride (12).

From the standpoint of scum cleaning ability, these components (a) are preferably contained in the composition of the present invention in an amount of 0.01 to 30% by weight, more preferably 1 to 10% by weight.

Examples of the sequestering agent of component (b) include
There is no particular limitation as long as it has the ability to chelate and block a metal ion, and examples thereof include hydroxycarboxylic acid or a salt thereof, and aminocarboxylic acid or a salt thereof.
Specific examples include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acids, tripolyphosphoric acid, ethyleneglycolbis (2-aminoethylether) tetraacetic acid, citric acid, and maleic acid. Acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid and salts thereof can be mentioned. Of these, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, citric acid or salts thereof are particularly preferable.

The component (b) is preferably blended in the composition of the present invention in an amount of 0.01 to 30% by weight, more preferably 1 to 3% by weight, from the viewpoint of scum cleaning ability.

The mixing ratio [(a) / (b)] of the component (a) and the component (b) is preferably 0.5 or more, more preferably 1 to 10, and particularly preferably 1. 5-
It is 5. When blended in this molar ratio, the scum cleaning ability is particularly enhanced.

When the composition of the present invention is further blended with a water-soluble solvent (c), the detergency against oil and fat stains is improved. The water-soluble solvent of the component (c) is not particularly limited, but compounds represented by the following general formulas (13) to (15), a dihydric alcohol having 4 to 12 carbon atoms and a carbon number of 1 to 1 are used. 5
One or more selected from monohydric alcohols are preferable.

[0041]

[Chemical 14]

(In the formula, 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 t is an integer of 0 to 10 and u is an integer of 0 to 10, except when both t and u 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 (13), when R ⁴ and R ⁵ are alkyl groups, the number of carbon atoms is preferably 1 to 4. In addition, in the formula (2), m and n of the average addition mole number of ethylene oxide (EO) and propylene oxide (PO) are 0 to 3, respectively. The order is not particularly limited and may be randomly added. Specific examples of the compound (2) 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 = 1) polyoxypropylene (p
= 1) 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 and diethylene glycol monobutyl ether are preferred from the viewpoints of detergency and feeling of use.

As the compound represented by the general formula (14), 1,3-dimethyl-2-imidazolidinone,
1,3-Diethyl-2-imidazolidinone is exemplified as a preferable example, and as the compound represented by the general formula (15), 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, isopropyl alcohol and the like. By blending these lower alcohols, the low temperature stability of the composition can be improved.

The water-soluble solvent as the component (c) is preferably added in the composition of the present invention in an amount of 0.1 to 20% by weight, more preferably 1 to 15% by weight, from the viewpoint of detergency against oil stains. Particularly preferably, the amount is 5 to 10% by weight.

The hard surface detergent composition of the present invention preferably further contains a nonionic surfactant for the purpose of further improving the detergency of oil and fat stains. 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, alkylene oxide addition alkyl group or alkenyl group-containing nonionic surfactant mixture, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensation One or more selected from surface-active agents and alkyl glycosides are preferable. More specific examples of such a nonionic surfactant include the following (1) to (11).

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

(3) Polyoxypropylene alkyl or alkenyl ethers in which the alkyl group or the alkenyl group has an average carbon number of 10 to 20 and the propylene oxide addition mole number is 1 to 20 moles on average. . (4) Polyoxybutylene alkyl or alkenyl ethers, wherein the alkyl group or alkenyl group has an average carbon number of 10 to 20, and the butylene oxide addition mole number is 1 to 20 moles on average. (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) is added to the nonionic surfactant mixture, wherein the alkyl group or the alkenyl group has an average carbon number of 10 to 20, and the number of moles of alkylene oxide added per molecule is on average. What is 1 to 30 mol. (6) A higher fatty acid alkanolamide represented by the following general formula (16) or an alkylene oxide adduct thereof.

[0049]

[Chemical 15]

[Wherein, R ⁹ is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R ¹⁰ and R ¹¹ are the same or different and are H or CH ₃ , v is an integer of 1 to 3, w Is 0
Is an integer of 3] (7) A sucrose fatty acid ester having an average carbon number of the fatty acid portion 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. Examples thereof include alkyl or alkenyl amine oxides having a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms. More preferable amine oxides include alkylamine oxides represented by the following general formula (a).

[0052]

[Chemical 16]

E is an alkylene group having 1 to 5 carbon atoms, a and b
Is a = 0 and b = 0, or a = 1 and b = 1] In the above general formula (a), R ¹² has 8 to 2 carbon atoms.
Although it is an alkyl group or an alkenyl group having 4 carbon atoms, an alkyl group having 12 to 18 carbon atoms is particularly preferable. R ¹³ and R ¹⁴ are alkyl groups having 1 to 3 carbon atoms, and a methyl group is particularly preferable. (10) A nonionic surfactant having a trade name of "Pluronic" obtained by condensing ethylene oxide. (11) Alkyl polysaccharide. For example, an alkyl polysaccharide represented by the following general formula, R ¹⁵ (OR ¹⁶ ) _x G _y [In the formula, R ¹⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkyl group. Represents 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]

The alkylglycoside represented by the above formula will be further described. In the formula, x has an average value of 0-5.
However, by changing this value, the water solubility and crystallinity of the hard surface cleaner composition used in the present invention can be adjusted. That is, the larger the value of x, the higher the water solubility and the lower the crystallinity. The value of x is preferably 0 to 2, and particularly preferably 0. On the other hand, y
When the average value is greater than 1, that is, when a sugar chain having two or more sugars is used as a hydrophilic group, the sugar chain bonding mode is 1-
2, 1-3, 1-4, 1-6 bond, and α-, β
It is possible to include any mixture with pyranoside or furanoside linkages and mixed binding modes thereof. The average value of y in the above formula is 1 to 5, preferably 1 to 1.5, more preferably 1.1 to 1.4. The method of measuring x is based on the proton NMR method. That is, since the proton in the alkyl glycoside belongs to the alkyl part proton, the anomeric proton, the oxygen root part proton and the hydroxyl group proton, y can be obtained from the integral ratio of the number of alkyl part protons on the NMR chart and the number of remaining protons. it can.

Further, R ¹⁵ in the formula is preferably an alkyl group having 10 to 14 carbon atoms from the viewpoint of solubility and detergency. Further, R ¹⁶ is preferably an alkylene group having 2 to 3 carbon atoms from the viewpoint of water solubility. Further, the structure of G is determined by a raw material of monosaccharide or disaccharide or more. As the raw material of G, monosaccharides include glucose, fructose, galactose, xylose, mannose, lyxose, arabinose, and a mixture thereof. Examples of the disaccharide or more include maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose, and mixtures thereof. Among these, preferred raw materials are glucose and fructose as monosaccharides, and maltose and sucrose as disaccharides or more, from the viewpoints of their availability and cost. Of these, glucose is particularly preferable from the viewpoint of easy availability.

Further, a 1-mole adduct of pentaerythritol / isostearyl glycidyl ether and a 1-mole adduct of sorbitol / isostearyl glycidyl ether,
At least 1 mol adduct of mannitol 2-octyldodecyl glycidyl ether, 1 mol adduct of methyl glucoside isostearyl glycidyl ether, 1 mol adduct of diglycerin isostearyl glycidyl ether, phytantriol, etc. Mention may be made of nonionic surfactants having one long-chain branched alkyl or alkenyl group and at least three hydroxyl groups.

Among these nonionic surfactants,
(1), (6), (9) and (11) are particularly preferable. Further, these nonionic surfactants are preferably added in the composition of the present invention in an amount of 0.5 to 40% by weight, particularly 5 to 20% by weight.

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

The composition of the present invention is produced by mixing the above components according to a conventional method, and the pH thereof is in the range of 3 to 10, more preferably 5 to 10, and particularly preferably 6 to 8. In a range other than this, problems such as rough hands occur, which is not preferable.

The composition of the present invention can be used as a cleaning agent for hard surfaces such as tiles, ceramics, enamel, reinforced plastics (FRP), stainless steel, wood, etc., but especially for cleaning bathrooms, bathtubs, bathtubs, that is, bathrooms. It is preferably used as a cleaning agent.

The cleaning method using the composition of the present invention is carried out by impregnating a sponge or the like with the composition and then scrubbing the surface to be cleaned in the bathroom or bath as in the case of conventional methods. Spray it on the clean surface, leave it for a while, and rinse it with water. In cleaning the bath, the composition of the present invention may be added to the residual water after bathing, allowed to stand for a certain period of time, preferably 1 hour or more, and then drained, after which the surface of the bath may be rinsed with water if necessary. In this case, the composition of the present invention has a cationic surfactant concentration of 0.5 to 100 ppm, preferably 10 to 80 ppm.

[0062]

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.

Example 1 A detergent composition having the composition shown in Table 1 was prepared and its detergency was evaluated. The results are shown in Table 1. The numbers in the table are% by weight
Indicates. (Evaluation method of detergency) Detergency is evaluated by gently adhering a cloth containing the detergent composition to a polypropylene floor hood and a floor chair that have stains on the bath that will not come off by rubbing for a few seconds. It was washed with water or sprayed on the stain and then lightly washed, and the state of removal of the stain was visually evaluated according to the following five grades. 5: Very good stain removal. 4: Good stain removal. 3: There is uneven stain removal. 2: Slightly stain removed. 1: Almost no dirt is removed.

[0064]

[Table 1]

It can be seen from Table 1 that the detergent composition of the present invention has a superior detergency as compared with the case where a conventional sodium alkylbenzenesulfonate is added. Also,
When the cleaning composition of the present invention was used, there was no damage to the material to be cleaned and almost no irritation to the skin.

[0066]

The cleaning composition of the present invention is excellent in the ability to decompose and solubilize metal stone Kenscum, so that it can quickly and easily clean dirt on hard surfaces such as bathrooms and bathtubs. .

Claims (5)

[Claims] 1. The following components (a) and (b): (a) a cationic surfactant represented by the general formula (1): [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents 1 carbon atom ~ 30
A linear or branched alkyl group or alkenyl group, an aralkyl group, an aryl group, , L, l ′, n and n ′ each represent a number of 0 to 3, and p, m and m ′ represent a number of 0 or 1 (however,
l, m and n or l ′, m ′ and n ′ cannot be 0 at the same time), A is And X represents a halogen atom or an alkylsulfate residue, and q represents the number of cations in the formula (1). (B) A hard surface cleaning composition containing a sequestering agent. 2. The composition according to claim 1, which further contains a water-soluble solvent. 3. The component (a) is represented by the following general formula (1a).
The composition according to claim 1 or 2, which is a quaternary ammonium salt selected from (1f). [Chemical 4] Wherein, r and s is the number of ^{1~6, R 1, R 2,} R
³ and X are the same as above] 4. The component (a) is represented by the general formula (1a) or (1
The composition according to claim 3, which is a quaternary ammonium salt selected from b) and (1c). 5. A cleaning composition for a bathroom, wherein the composition is a bathroom cleaning composition.
The composition according to any one of 1.