JPH0867898A - Solid cleaning agent for flush toilet - Google Patents

Abstract

PURPOSE: To obtain the subject cleaning agent, containing a polyoxyethylene fatty acid monoethanolamide as a detergent active component, capable of keeping the active component concentration in a water storage tank constant and excellent in operating efficiency such as easy formability. CONSTITUTION: This solid cleaning agent contains a polyoxyethylene fatty acid monoethanolamide of formula I [R is a 9-19C alkyl or alkenyl; (n) is an integer of 1-10] [e.g. polyoxyethylene (2) lauric acid monoethanolamide or polyoxyethylene (2) myristic acid monoethanolamide]. A block copolymer of formula II [(x+z) is an integer of 50-300: (y) is an integer of 5-70] is preferably added to the compound of formula I. For example, a polyoxyethylene (150) polyoxypropylene glycol (35) is cited as the block copolymer of formula II. The blending ratio of the compound of formula I to the polymer of formula II is preferably (1:9) to (8:2).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solid detergent for flush toilets. More specifically, it relates to a cleaning agent for flush toilets, which contains polyoxyethylene fatty acid monoethanolamide as a cleaning active ingredient.

[0002]

2. Description of the Related Art Conventional solid detergents for flush toilets are
There are a type put in a container to suppress the elution rate of a surfactant and the like, and a type put in a water tank directly. A type put in a water tank directly has been widely used because of its easy handling.

However, this type of direct-injection type detergent is required to release the minimum necessary amount of active ingredients such as surfactants and dyes into the water tank in a short time and keep the concentration constant for a long time. Although it is a condition, it has a drawback that it is difficult to keep the concentration of the active ingredient constant. Then, for the purpose of solving such a drawback, various combinations with a polymer substance or the like whose water solubility is adjusted have been proposed.

For example, a combination of polyalkylene glycol, polyoxyethylene alkyl ether, or polyoxyethylene aryl ether with a surfactant, a dye and a fragrance (JP-A-54-81310), water-soluble sodium polyacrylate, etc. A thickener, a water-swellable polymer substance obtained by emulsion-polymerizing polyvinyl alcohol and acrylic acid to prevent the detergent from being rapidly eroded during the immersion (JP-A-57-38899), polyoxyethylene (50 to 500). ) Alkyl ether (JP-A-57-17
9298), polyoxyethylene (30-300) dialkyl ester (JP-A-58-25398), and the like, which are based on a block polymer of propylene oxide and ethylene oxide (JP-A-1-110599). No.) etc. have been proposed.

However, in these methods, there is still no sufficient effect in that the concentration in the reservoir is kept constant by merely suppressing the elution rate, and when a polymer substance is added to further suppress the elution rate, There are also drawbacks such as an increase in melt viscosity of the system and a decrease in workability during molding.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a minimum amount of activator in a water storage tank of a flush toilet in a short time.
Providing a solid detergent for flush toilets that releases active ingredients such as dyes and keeps their concentration constant for a long time, that is, drains with no difference in concentration of active ingredients between flushes, and has good workability during manufacturing It is to be.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventor has found that by using polyoxyethylene fatty acid monoethanolamide, the concentration of the active ingredient in the water tank can be increased over a long period of time. The present invention has been completed by finding that a solid detergent for flush toilets which can be kept constant and has excellent workability during production can be obtained.

That is, the present invention is based on the general formula (1)

[0009]

[Chemical 4]

(Wherein R represents a linear or branched alkyl or alkenyl group having 9 to 19 carbon atoms and n represents an integer of 1 to 10). The present invention relates to a solid detergent for flush toilets, which comprises ethanolamide.

The polyoxyethylene alkylolamide used in the present invention is represented by the above general formula (1), in which R is
Is a linear or branched alkyl group or alkenyl group having 9 to 19 carbon atoms. The alkyl group or alkenyl group, for example, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, etc. It is a base. In the general formula (1), n, which represents the number of moles of ethylene oxide added, is in the range of 1 to 10. However, when it exceeds 10, the water solubility increases, and a constant elution amount cannot be maintained, which is not preferable.

Specific examples of the polyoxyethylene fatty acid monoethanolamide represented by the general formula (1) include polyoxyethylene (2) lauric acid monoethanolamide and polyoxyethylene (2) myristic acid monoethanolamide. , Polyoxyethylene (5) myristic acid monoethanolamide, polyoxyethylene (2)
Examples include palmitic acid monoethanolamide.

In the solid detergent for flush toilet of the present invention, the compounding amount of polyoxyethylene fatty acid monoethanolamide is 1 to 60% by weight based on the solid detergent.
If it is less than 10% by weight, it is difficult to keep the solid elution of the solid detergent stable, and the melt viscosity is insufficiently lowered to lower the workability, and further, the peelability from the molding container at the time of molding is lowered. It is not preferable, and even if it exceeds 60% by weight, the solid detergent becomes soft and it is not preferable in terms of moldability.

The polyoxyethylene fatty acid monoethanolamide used in the solid detergent for flush toilet of the present invention has the effect that the concentration in the water tank of the flush toilet becomes constant in a short time, and excessively. Since it does not elute, the dye and other active ingredients can be released over a long period of time.

As a result of further research, the inventor found that
It was found that a more excellent solid detergent for flush toilets can be obtained by using polyoxyethylene fatty acid monoethanolamide in combination with a specific block polymer.

That is, the second invention is based on the general formula (1)

[0017]

[Chemical 4]

(Wherein R represents a linear or branched alkyl or alkenyl group having 9 to 19 carbon atoms, and n represents an integer of 1 to 10). Monoethanolamide and general formula (2)

[0019]

[Chemical 5]

(Where x + z is an integer of 50 to 300, y
Is an integer of 5 to 70), and relates to a solid detergent for flush toilets characterized by containing a block polymer.

In the second invention, the block polymer used in combination with the polyoxyethylene fatty acid monoethanolamide is the compound represented by the general formula (2), which is a copolymer of propylene oxide and ethylene oxide. , X, y, z representing the degree of polymerization of ethylene oxide or propylene oxide in the general formula (2)
However, if it is out of the above range, solidification becomes difficult, which is not preferable.

Specific examples of the block polymer represented by the general formula (2) used in the present invention include polyoxyethylene (150) polyoxypropylene glycol (3).
5), polyoxyethylene (50) polyoxypropylene glycol (40), polyoxyethylene (200)
Examples thereof include polyoxypropylene glycol (40), polyoxyethylene (300) polyoxypropylene glycol (55), polyoxyethylene (200) polyoxypropylene glycol (70), and the like.

These block polymers may be used alone or in two.
A combination of two or more species can be used.

In the second aspect of the present invention, the mixing ratio of the polyoxyethylene fatty acid monoethanolamide and the block polymer in the detergent needs to be in the range of 1: 9 to 8: 2 by weight. When the compounding ratio of the polyoxyethylene fatty acid monoethanolamide to the block polymer is more than this range, the tablet is soft and the moldability is poor. On the other hand, when the compounding ratio is less than this range, the concentration stabilizing action, the viscosity decrease at the time of melting, the molding Is unsuitable because the releasability is deteriorated. A particularly preferred range is 2: 8 to 4: 6.

By using the polyoxyethylene fatty acid monoethanolamide and the block polymer together in the above proportion, the polyoxyethylene fatty acid monoethanolamide itself does not impair the effect of the concentration of the polyoxyethylene fatty acid monoethanolamide being constant in the water tank in a short time. In addition, the viscosity at the time of melting is reduced, and the releasability at the time of molding becomes good. The cause is not necessarily clear, but the polyoxyethylene fatty acid monoethanolamide itself has good peelability when heated to 30 to 40 ° C.,
It is considered that it interacts with the block polymer to improve the peelability of the block polymer.

In the solid detergent for flush toilet of the present invention, if necessary, perfumes, pigments, surfactants, water-soluble polymers, bactericides,
Preservatives, builders and the like can also be added.

The solid detergent for flush toilet of the present invention can be prepared by a conventional method. That is, the raw material can be heated and melted and poured into a mold to be cooled and solidified, or can be extruded to obtain a product.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples.

Examples 1 to 3 and Comparative Examples 1 to 4 Solid cleaners for flush toilets formed by melt-mixing the components of the compositions shown in Table 1 and then cooling and solidifying in a cylinder with a rubber stopper. The viscosity, releasability, and elution degree of each were determined. Table 2 shows the results. The degree of dissolution is shown in FIG. 1 in a graph for easier understanding.

The viscosity of the composition, the releasability from the mold, and the elution degree were determined as follows.

(1) Viscosity The viscosity at 50 ° C. when each component was mixed and melted was measured with a B-type viscometer (manufactured by Tokyo Seiki Co., Ltd.).

(2) Peelability Each component was put in a cylinder of SUS304 having an inner diameter of 24 mm, heated, melted, cooled, put in a constant temperature bath at 40 ° C., and the force at the time of extrusion was measured by a rheometer. I made an evaluation.

A: It can be extruded with a force of 30 g / cm ² or less B: It can be extruded with a force of 80 g / cm ² or less C: It can be extruded with a force of 160 g / cm ² or more (3) Elution degree 15 g of detergent Immerse in 1 liter of tap water kept at ℃, stir every 1 hour, put the solution in a glass cell with an optical path length of 1 cm, measure the absorbance at a wavelength of 630 nm, measure the elution amount from the calibration curve, and clean before immersion. It was calculated as a ratio (%) to the amount of the agent.

[0034]

[Table 1]

[0035]

[Table 2]

From the results shown in Table 2, the solid detergent comprising the polyoxyethylene fatty acid monoethanolamide of the present invention and the solid detergent comprising the polyoxyethylene fatty acid monoethanolamide and the block polymer in combination have a low melt viscosity and a peeling property. It is confirmed that the product has good workability during production, and that even when subjected to the dissolution test, it is stably eluted without being eluted in a large amount at one time. On the other hand, the solid detergent composed of the block polymer alone or other polyoxyethylene derivative has a high melt viscosity or low peeling property, and a large amount is eluted even in the dissolution test, and thus as a solid detergent for flush toilets. It was inappropriate.

Example 4 60 g of a solid detergent for a flush toilet having the following composition was produced and put into a water tank of the flush toilet for use.
During production, this solid detergent had a low viscosity when melted and was excellent in releasability from the molding frame. When actually used, a stable dye was eluted for one month or more.

Ingredient name Weight% (1) Polyoxyethylene (2) Lauric acid monoethanolamide 12 (2) Polyoxyethylene (154) Polyoxypropylene glycol (20) 47 (3) Polyethylene glycol 6000 20 (4) Glauber's salt 10 (5) Polyoxyethylenesorbitan monolaurate (20E.O.) 3 (6) Dye (Blue No. 1) 3 (7) Perfume 5

[0039]

EFFECT OF THE INVENTION The solid detergent for flush toilet of the present invention has a low melt viscosity in the manufacturing process and is excellent in mold release at the time of molding so that it can be easily molded, and a required amount in a short time in a flush water storage tank can be obtained. It can be used for a long period of time from the initial stage to the final stage without changing its performance due to its property of maintaining its concentration without dissolving more than necessary and proceeding further than necessary.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the elution degree of solid detergents of Examples and Comparative Examples and time.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R represents a linear or branched alkyl group or alkenyl group having 9 to 19 carbon atoms, and n is 1 to 1
A solid detergent for flush toilets, comprising a polyoxyethylene fatty acid monoethanolamide represented by the formula (indicated by an integer of 0). 2. A compound represented by the general formula (1): (In the formula, R represents a linear or branched alkyl group or alkenyl group having 9 to 19 carbon atoms, and n is 1 to 1
A polyoxyethylene fatty acid monoethanolamide represented by the general formula (2): (In the formula, x + z is an integer of 50 to 300, y is an integer of 5 to 70) A solid detergent for flush toilets, comprising a block polymer.