JPH0860186A - Detergent composition for flush toilet - Google Patents

Abstract

PURPOSE: To obtain a detergent composition for flush toilets excellent in uniform solubility, expressing excellent detergency for a long time and containing an anion surfactant such as an alkylsulfuric acid ester, etc., a water soluble polymer having a specific molecular weight and a water soluble organic solvent having a specific HLB. CONSTITUTION: This detergent composition for flush toilets is obtained by blending (A) an anion surfactant such as a salt of an alkylsulfuric acid ester, an alkylsulfonic acid salt, an alkylarylsulfonic acid salt, a polyoxyalkylene alkyl ether sulfuric acid salt, etc., and (B) as a water soluble polymer having >=100,000 molecular weight, a polymer or copolymer of >=1 carboxylic acid units expressed by formula I (X, Y and Z are each H, an alkyl, an aryl, hydroxy, a hydroxyalkyl, carboxyl, an alkoxycarbonyl) or a copolymer thereof with units of formula II (R<1> is H or a 1-10C alkyl) and formula III [R<2> is CONHR<3> (R<3> is the same as R<1> ) or COOR<4> (R<4> is the same as R<1> )], etc., and (C) a water soluble organic solvent having >=7 HLB.

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 flush toilets which is excellent in detergency and durability.

[0002]

2. Description of the Related Art Soft stools tend to adhere to the surface of flush toilets,
The loose stools thus attached are difficult to remove by washing with water without using mechanical force. Therefore, conventionally, the active ingredient is released into the flush water from the flush auto cleaner (toilet bowl auto cleaner) installed in or on the water storage tank of the flush toilet to continuously prevent the accumulation of dirt on the flush toilet and clean it. A cleaning composition has been used which is effective and keeps clean.

As described above, the detergent composition for flush toilets is strongly required to have sustainability in addition to detergency because of the necessity of continuously releasing the active ingredient into the flush water. A toilet cleaning block having improved durability by combining a surfactant and a viscosity modifier has been reported (WO92 / 03532).

[0004]

However, this toilet cleaning block is not yet sufficiently durable, and when an anionic surfactant and a viscosity modifier are molded into a block, a uniform composition is obtained. Since it is difficult, fragments and cracks flow out, and there is a drawback that uniform sustainability cannot be obtained. Therefore, an object of the present invention is to provide a detergent composition for flush toilets, which is uniformly dissolved and has a long-lasting effect.

[0005]

Under such circumstances, the present inventor has conducted diligent studies and as a result, in addition to a specific anionic surfactant and a water-soluble polymer having a molecular weight of 100,000 or more, an HLB of 7 or more. The present invention has been completed based on the finding that by combining a water-soluble organic solvent, it is possible to obtain a detergent for flush toilets which is more uniformly dissolved and more durable than conventional detergents for flush toilets.

That is, the present invention provides the following component (A),
(B) and (C): (A) Anionic surfactant selected from alkyl sulfate ester salt, alkyl sulfonate, alkylaryl sulfonate and polyoxyalkylene alkyl ether sulfate ester salt, (B) molecular weight of 100,000 or more. And a water-soluble polymer (C) and a water-soluble organic solvent having a HLB of 7 or more (C).

Examples of the alkyl moiety of the anionic surfactant as the component (A) used in the present invention include a linear or branched alkyl group having 6 to 24 carbon atoms.
To 24 branched chain alkyl groups are more preferable, and the number of carbon atoms is 6 to
Eighteen branched chain alkyl groups are particularly preferred. Examples of this branched chain alkyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group, isododecyl group, isotridecyl group,
Isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group,
Examples thereof include a 2-ethylhexyl group, and among these, an isododecyl group and an isohexadecyl group are particularly preferable.

Examples of the aryl moiety of the alkylaryl sulfonate include phenyl and naphthyl, with phenyl being particularly preferred.

The polyoxyalkylene group includes polyoxyethylene, polyoxypropylene, and mixed types thereof, with polyoxyethylene being particularly preferred. The degree of polymerization of polyoxyalkylene is 1 to 50.
Are preferred, 2-10 are more preferred, and 3-8 are particularly preferred.

Further, as salts of these surfactants,
Alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; metal salts such as iron, copper and zinc; amine salts such as ammonium, monoethanolamine salt, diethanolamine salt and triethanolamine salt Can be mentioned. Among the components (A), a particularly preferable specific example is a sodium salt.

Of the above-mentioned surfactant salts, the component (A) is preferably an alkyl sulfate ester salt or a polyoxyalkylene alkyl ether sulfate ester salt,
Alkyl sulfate ester salts are particularly preferable.

The above component (A) is contained in the composition of the present invention such that the component (A) is released into the flush water in an amount sufficient to exhibit the antifouling effect and the cleaning effect when the composition of the present invention is used. Compound. It is sufficient if the effective concentration of the component (A) in flash water is 0.5 ppm or more,
More preferably, it is 100 ppm. In order to mix the component (A) so as to have such an effective concentration, it is usually 20 in the composition of the present invention, although it depends on the amount of the component (B).
.About.85% by weight (hereinafter referred to simply as "%"), especially 35 to 70
%, More preferably 45 to 60%.

The water-soluble polymer as the component (B) is not particularly limited as long as it has a molecular weight of 100,000 or more (particularly preferably 150,000 to 5,000,000), and it may be used in a linear or crosslinked type. it can. For example, natural polymers such as guar gum, konjac mannan, carrageenan, alginic acid, gum arabic, pectin and agar; semi-synthetic polymers such as sodium cellulose sulfate, carboxymethyl cellulose and hydroxypropyl methyl cellulose;
Although any of synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid can be used, those having a carboxyl group or a sulfuric acid group, especially the use of a small amount of the synthetic polymer can improve the detergency of the component (A). It is preferable because it does not inhibit.

Examples of the water-soluble polymer having a sulfate group include sodium cellulose sulfate, carrageenan and agar.

As the water-soluble polymer having a carboxyl group, a polymer or copolymer composed of one or more carboxylic acid units represented by the following general formula (1),
Alternatively, a copolymer comprising this carboxylic acid unit and a monomer unit represented by the following general formula (2) and a monomer unit represented by the following formula (3) can be mentioned. .

[0016]

[Chemical 4]

(In the formula, X, Y and Z are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, a hydroxyalkyl group, a carboxyl group or an alkoxycarbonyl group.)

[0018]

[Chemical 5]

(In the formula, R ¹ is a hydrogen atom and has 1 to 1 carbon atoms.
0, preferably an alkyl group having 1 to 3 carbon atoms or an acyl group. )

[0020]

[Chemical 6]

(In the formula, R ² is CONHR ³ or COOR ⁴
(Here, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁴ is an alkyl group having 1 to 10 carbon atoms). )

Preferred examples of the carboxylic acid unit of the above formula (1) include those represented by the following formula.

[0023]

[Chemical 7]

In the formula (2), R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom. In formula (3), R ² is preferably a methoxycarbonyl group.

Examples of such a water-soluble polymer having a carboxyl group include xanthan gum, alginic acid and polyacrylic acid, and it is particularly preferable to use crosslinked polyacrylic acid having a molecular weight of 1 to 5,000,000.

The proportion of the component (A) and the component (B) used is such that the content of the component (A) in the detergent composition is 20-.
85%, the content of the component (B) is 0.1 to 25%, and the weight ratio of the component (A) to the component (B) is A / B = 1 to 99.
It is preferable that the amount is 0, particularly the content of the component (A) is 35 to 70%, and the content of the component (B) is 1 to 15%.
%, A / B = 3 to 100 is more preferable.

In the composition of the present invention, the above-mentioned component (A)
By adding a water-soluble organic solvent having an HLB of 7 or more as the component (C) to the component (B), the component (A) can be uniformly mixed and dispersed in the component (B), resulting in uniform dissolution and good Sustainability is obtained. The addition of a water-soluble organic solvent having an HLB of less than 7 is not preferable because the detergency is lowered and the composition becomes insoluble in water. Here, in the present invention, the water-soluble organic solvent means a polar or non-polar organic solvent which can be uniformly mixed with water, and HL
It is not particularly limited as long as it is B7 or more, but does not include water. The HLB here is H of Davies.
LB (Congress of Surface Ac
(ivity 1, 426, 1957).

As the water-soluble organic solvent (C), alcohol having 1 to 4 carbon atoms, diol having 2 to 8 carbon atoms, polyol having 3 to 8 carbon atoms, monoalkyl ether of (poly) alkylene glycol and (poly) ) It is preferable to use one kind or two or more kinds selected from the group consisting of alkylene glycol monoesters. Here, examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol and the like. Examples of the diol having 2 to 8 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and hexylene glycol. Carbon number 3
Examples of the polyols of to 8 include glycerin, trimethylolpropane and the like. Examples of the (poly) alkylene glycol include those represented by the formula HO (R ⁵ O) _n H [wherein R ⁵ represents an alkylene group having 2 to 4 carbon atoms, and n represents a number of 1 to 4]. Further, as the monoalkyl ether of (poly) alkylene glycol,
Formula R ⁶ O (R ⁵ O) _m H [wherein R ⁶ is an alkyl group having 1 to 8 carbon atoms, m is a number of 1 to 30, and R ⁵ is the same as above]
The thing represented by is mentioned. Among these components (C), monoalkyl ether of (poly) alkylene glycol is particularly preferable.

The content of the component (C) in the composition of the present invention is preferably 5 to 40%, particularly 10 to 25% from the viewpoint of uniform solubility and sustainability.

In the composition of the present invention, in addition to the above essential components, an excipient such as an alkali metal salt of an acid such as sulfuric acid, carbonic acid, boric acid, phosphoric acid, an alkaline earth metal salt, an ammonium salt or silicic acid anhydride. A chelating agent such as hydroxycarboxylic acid, a fragrance, a germicide, an antiseptic, a solidifying agent, a thickener, a dye, a bleaching agent, a releasing agent, a solvent, an antifoaming agent, a surfactant other than the component (A), etc. Can be blended.

Preferred examples of formulation of the composition of the present invention include:
Ingredient (A) 35-70%, Ingredient (B) 0.1-25%,
Ingredient (C) 10-25%, fragrance 3-10%, pigment 1-5
%.

The composition of the present invention can be used by blending the above-mentioned components and preparing it in the form of solid, granule, paste or liquid according to a conventional method. For example, in order to prepare a solid preparation, it is preferable to heat and dissolve each of the above components as necessary, mix, cool and solidify, and mold into a desired shape. In addition, the composition of the present invention is usually used as a preparation of 15 to 150 g, preferably 20 to 70 g, by being installed in or on the tank of a flush toilet.

[0033]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 12 and Comparative Examples 1 to 5 The compositions shown in Table 1 were prepared, and the sustainability and uniform solubility were evaluated by the following test methods.

[Production Method of Composition] Each component was mixed with a kneader, injected into a noodle shape with an extruder, and then molded with a stamping machine.

[Test Method] (1) Sustainability 50 g of a solid molded product of the test composition was bottomed in a low tank, flash was repeated 17 times a day, and the required number of days until completely dissolved was recorded. .

(2) Uniform Solubility During the sustainability measurement period, the dye concentration of Blue No. 1 when quantified in flash water at 630 nm was measured, and the variation range was defined as the uniform solubility. During the period, when the ratio of the number of days outside the range of 0.1 ppm to 1 ppm was within 50%, it was considered that the uniformity was good. This judgment is generally performed when the dye concentration is 0.1 pp.
This is because when it is less than m, it feels light, and when the dye concentration exceeds 1 ppm, it feels dark.

[Test Results] The results obtained are shown in Tables 1 and 2.
Shown in In the table, it can be judged that the uniform solubility is practically excellent when there is no outflow or adhesion of fragments and the sustainability is 30 days or more. As is clear from Table 1, the composition of the present invention was superior to the comparative composition in both sustainability and uniform solubility.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

EFFECTS OF THE INVENTION Since the cleaning composition for flush toilets of the present invention has good durability and dissolves uniformly, it is excellent for long-term toilet cleaning simply by installing it in or on the water storage tank. Shows the action.

Claims (6)

[Claims] 1. The following components (A), (B) and (C): (A) selected from alkyl sulfate salts, alkyl sulfonates, alkylaryl sulfonates and polyoxyalkylene alkyl ether sulfate ester salts. A cleaning composition for a flush toilet, which contains an anionic surfactant, (B) a water-soluble polymer having a molecular weight of 100,000 or more, and (C) a water-soluble organic solvent having an HLB of 7 or more. 2. The cleaning composition for flush toilets according to claim 1, wherein the component (B) is a polymer having a carboxyl group or a sulfuric acid group. 3. The component (B) has the following general formula (1): (In the formula, X, Y and Z are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, a hydroxyalkyl group, a carboxyl group or an alkoxycarbonyl group.) A polymer or copolymer composed of two or more kinds, or the carboxylic acid unit and the following general formula (2): (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group.) And the following general formula (3): (In the formula, R ² is CONHR ³ or COOR ⁴ (where R ³
Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms). The cleaning composition for flush toilets according to claim 1 or 2, which is a copolymer comprising a monomer unit selected from the group consisting of (1) and (3). 4. The component (B) has a molecular weight of 1,000,000 to 500.
The cleaning composition for flush toilets according to claim 1 or 2, which is a cross-linked polyacrylic acid. 5. The component (C) is an alcohol having 1 to 4 carbon atoms, a diol having 2 to 8 carbon atoms, a polyol having 3 to 8 carbon atoms, a (poly) alkylene glycol and a monoalkyl ether of (poly) alkylene glycol. The cleaning composition for flush toilets according to any one of claims 1 to 4, which is one kind or two or more kinds selected from the group consisting of: 6. The component (A) is selected from a branched alkyl sulfate ester salt, a branched alkyl sulfonate salt, a branched alkyl aryl sulfonate salt and a polyoxyalkylene branched alkyl ether sulfate ester salt. The cleaning composition for flush toilets according to any one of 1.