JPH06330096A - Fragrance cleaner composition for flush toilet - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a fragrance cleaner composition for flush toilets, which has a long elution time of compounding ingredients such as fragrances and colorants, has excellent slow-dissolving property, and has excellent shape retention and adhesiveness. [Structure] Polyethyleneimine having 10 to 200 active hydrogens, a branched structure containing primary, secondary, and tertiary amino nitrogen, and a number average molecular weight of 400 to 10,000, or a derivative thereof, has 3 carbon atoms. Ethylene oxide-added polyether compound having a number average molecular weight of 5,000 to 600,000, which is obtained by subjecting an epoxide of -40 to an ethylene oxide in a weight ratio of an epoxide of 3 to 40 carbons / ethylene oxide in a ratio of 0/100 to 50/50. In addition, from 40 to 85% by weight of a polyether compound, 1 to 25% by weight of a coloring agent and 1 to 30% by weight of a fragrance, which are obtained by adding 0.4 to 10 moles of an epoxide having 8 to 40 carbon atoms to 1 mole of the hydroxyl group. A fragrance cleaner composition for flush toilets.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aroma cleaner composition for flush toilets. More specifically, it relates to an aroma cleaner composition for flush toilets, which has a long dissolution disappearance time.

[0002]

2. Description of the Related Art Aroma cleaners for flush toilets are generally solid and can be stored in a container, or can be put directly into the water tank of the flush toilet or attached to the hand washing part of the water tank as they are. Therefore, the composition is gradually dissolved or dispersed in the stored water in the tank, the toilet bowl of the flush toilet is washed with running water at the time of flushing, and the aroma is drifted, so as to keep the toilet refreshing. It is used.

The fragrance cleaner for flush toilets comprises a cleaning component, a fragrance component and a colorant. Most of the cleaning ingredients are solid, and as a base of the fragrance cleaner composition for flush toilets, they have the role of solidifying and also control the dissolution rate of the compounding ingredients in running water and stored water to provide a suitable aromaticity. And it has the role of maintaining detergency for an appropriate period.

As a base for such an aroma cleaner for flush toilets, polyethylene glycol (Japanese Patent Laid-Open No. 53-3170) is used.
No. 8), ethylene oxide polymers such as propylene oxide-ethylene oxide copolymer (JP-A-51-39705); polyalkylene glycols such as polyethylene glycol in which the terminal hydroxyl groups are hydrophobized with alkyl groups or acyl groups. Glycol derivative (JP-A-57-179298, JP-A-58-2539)
No. 8); a urethane compound obtained by reacting a polyoxyalkylene compound and an organic polyisocyanate (JP-A-55-131098); obtained by subjecting a polyoxyethylene compound and a dicarboxylic acid to a condensation reaction. Diester compound (Japanese Patent Laid-Open No. 59-230081)
Are known.

However, the bases of the conventional fragrance cleaners for flush toilets have the following problems.

That is, polyethylene glycol and propylene oxide-ethylene oxide copolymer have problems that the water solubility is too large, so that the slow-dissolving property and sustainability are poor and the life of the fragrance cleaner is short.

Further, a polyalkylene glycol derivative,
Urethane compounds and diester compounds are not sufficiently soluble and durable. Furthermore, the water solubility depends on the water temperature, and there is a problem that the sustainability is significantly different between summer and winter. In addition, if it is immersed in water for a long time, the shape may be destroyed or destroyed, the aroma components and colorants may not be eluted uniformly, and water-insoluble components may occur, resulting in muddy cleaning water. .

Further, when a molded body of the fragrance cleaner composition for flush toilets is put into a tank for use, the molded body sinks and remains in the tank, and flush water is flushed from the tank. Since it is necessary to prevent the molded body from moving due to the movement of water when replenishing the water, development of an aromatic cleaning composition for flush toilets, which has adhesiveness to the inner wall of the tank and has a long life, is awaited. Has been.

[0009]

Therefore, in view of the above-mentioned prior art, the inventors of the present invention have taken a long time to elute the blended components such as a fragrance component and a coloring component. As a result of earnest research to develop a fragrance cleaner composition for flush toilets that has excellent shape retention and adhesion when soaked, finally found a fragrance cleaner composition for flush toilets having excellent properties It came to complete the invention.

[0010]

The present invention provides (A) (a)
It has 10 to 200 active hydrogens, has a branched structure containing primary, secondary and tertiary amino nitrogen, and has a number average molecular weight of 400 to
10 to 200 of 10000 polyethyleneimine or active hydrogen
The above polyethyleneimine derivative has 3 carbon atoms
˜40 epoxide and ethylene oxide in a weight ratio of 0 to 100 epoxide / ethylene oxide having 3 to 40 carbon atoms
Number average molecular weight of 5000, which is obtained by addition reaction at a ratio of 50/50
To the ethylene oxide-added polyether compound having (b) to 600,000, and (b) an epoxide having 8 to 40 carbon atoms per one hydroxyl group of the ethylene oxide-added polyether compound 0.4.
~ Polyether compound by addition reaction of 10 mol 40 ~
It relates to a fragrance cleaner composition for flush toilets, which comprises 85% by weight, (B) 1 to 25% by weight of a coloring agent, and (C) 1 to 30% by weight of a perfume.

[0011]

ACTIONS AND EXAMPLES The aroma cleaner composition for flush toilets of the present invention comprises polyethyleneimine or a polyethyleneimine derivative as a base, ethylene oxide or ethylene oxide and an epoxide having 3 to 40 carbon atoms (hereinafter referred to as epoxide (A)). And an ethylene oxide-added polyether compound obtained by addition reaction with an epoxide having 8 to 40 carbon atoms (hereinafter, referred to as epoxide (B)) are added to the polyether compound (hereinafter, simply referred to as polyether compound) (Component (A)) is contained.

The polyethyleneimine has 10 to 200 active hydrogen atoms in one molecule and has a number average molecular weight of 400 to
10000, preferably 12 to 10 active hydrogens per molecule
One having 0 and a number average molecular weight of 500 to 5000 can be mentioned. When the number of active hydrogens in one molecule is less than 10 and the number average molecular weight is less than 400, the solubility and the adhesion to the inner wall of the tank when immersed in water and the shape retention are good. It becomes difficult to obtain an aroma cleaner composition for flush toilets. When the number of active hydrogen exceeds 200 and the number average molecular weight exceeds 10,000, the viscosity of polyethyleneimine becomes too high and the addition reaction with ethylene oxide or the like becomes difficult.

The polyethyleneimine does not have a completely linear structure but has a branched structure containing primary, secondary and tertiary amino nitrogen. The ratio of several primary, secondary, and tertiary amino nitrogen atoms contained in one molecule is 1: 1 to 1: 2.5: 1 in order, respectively. It is preferable from the viewpoints of sustained dissolution and sustainability of the agent composition.

As the polyethyleneimine derivative,
The number of active hydrogen present in one molecule is 10 to 200, and 1
Having a branched structure containing secondary, secondary and tertiary amino nitrogen and having a number average molecular weight of 400 to 10,000, preferably 12 to 100 active hydrogens and a number average molecular weight of 500 to 5,000. Used.

As a typical example of such a polyethyleneimine derivative, for example, a reaction product of the above-mentioned polyethyleneimine with aldehydes such as acetaldehyde, butyraldehyde, capryl aldehyde, laurin aldehyde, etc., and ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, etc. Reaction product of polyethyleneimine with an alkyl halide such as methyl chloride, methyl bromide, ethyl chloride, hexyl chloride, octyl chloride, lauryl chloride, benzyl chloride and cetyl bromide; polyethyleneimine and methyl isocyanate, isobutyl isocyanate, phenyl isocyanate, Reaction products with isocyanates such as lauric isocyanate and stearyl isocyanate; polyethylene Reaction products of min with a compound having an active double bond such as acrylonitrile, butadiene, acrylic acid and butyl acrylate; reaction products of polyethyleneimine with urea; polyethyleneimine with acetic acid, caproic acid, lauric acid, stearin Acids, carboxylic acids such as oleic acid, ricinoleic acid, acetic anhydride, propionic acid anhydride, benzoic acid anhydride, succinic acid anhydride, maleic acid anhydride, acid anhydrides such as phthalic acid anhydride, propionic acid chloride, caproic acid chloride, lauric acid Chloride, stearic acid chloride, oleic acid chloride,
Examples include reaction products with acyl halides such as lauric acid bromide.

Specific examples of the epoxide (A) include:
For example, propylene oxide, butylene oxide, butene oxide, styrene oxide and 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxyoctadecane, 1,2-epoxydocosane, 1, 2-epoxy octacosane, 1,2-
Epoxides alkylene oxides such as long chain epoxides such as triacontane; phenyl glycidyl ether,
Examples thereof include glycidyl ethers such as n-hexyl glycidyl ether and n-octyl glycidyl ether, but the present invention is not limited to these examples. In addition, these can be individual or can use 2 or more types together.

The use ratio of the epoxide (A) and ethylene oxide is such that the epoxide (A) / ethylene oxide (weight ratio) is 0/100 to 50/50, preferably 5/95 to 40.
/ 60. If the usage ratio exceeds 50/50,
The melting point of the finally obtained base material becomes too low, and the moldability of the fragrance detergent composition for flush toilets into molded articles becomes poor.

The addition reaction of ethylene oxide or epoxide (A) to the polyethyleneimine or the polyethyleneimine derivative is carried out, for example, by using the starting material polyethyleneimine or the polyethyleneimine derivative as a basic substance such as sodium hydroxide, potassium hydroxide or sodium methylate. It can be carried out by a usual method such as a method of reacting by adding ethylene oxide and, if necessary, epoxide (A) at 100 to 180 ° C. in the presence of a catalyst.

The use ratio of ethylene oxide and optionally epoxide (A) to the polyethyleneimine or the polyethyleneimine derivative is not particularly limited, and may be appropriately adjusted according to the performance of the intended fragrance cleaner composition for flush toilets. It is good, but from the viewpoint of moldability,
It is preferably 10 to 300 mol, especially 20 to 200 mol, per 1 mol of active hydrogen of polyethyleneimine or a polyethyleneimine derivative.

When the epoxide (A) is used, the order of addition of the epoxide (A) and ethylene oxide is not particularly limited, and thus the obtained ethylene oxide-added polyether compound is epoxide (A) and ethylene oxide. Block copolymer with
Random copolymers, or any of them may be added first, but from the viewpoint of the sustained solubility and moldability of the fragrance cleaner composition for flush toilets, after block-polymerizing the epoxide (A), A copolymer obtained by block-polymerizing ethylene oxide is preferable.

The number average molecular weight of the ethylene oxide-added polyether compound is 5,000 to 600,000, preferably 5,000.
It is ~ 400,000. When the number average molecular weight is less than 5000, the melting point of the finally obtained base is lowered, the moldability of the fragrance detergent composition for flush toilets is lowered, and when it exceeds 600,000, ethylene oxide is used. Not only is the viscosity of the addition polyether compound increased, which requires a long time for production and is economically disadvantageous, but the viscosity of the finally obtained base is also increased. Mixing becomes difficult.

The above-mentioned polyether compound is a compound obtained by subjecting an ethylene oxide-added polyether compound to an addition reaction of an epoxide (B) as described above.

The epoxide (B) can be used without particular limitation as long as it is an epoxide having 8 to 40 carbon atoms.
From the viewpoint of sustainability and shape retention when immersed in water, those having 12 to 22 carbon atoms are preferable. The carbon number is 8
When it is less than 40%, the slow-dissolving property of the fragrance cleansing composition for flush toilets becomes low, and when it exceeds 40, the shape is apt to be broken or it is easily broken when immersed in water.

Specific examples of the epoxide (B) include:
For example, styrene oxide, 1,2-epoxyoctane having an epoxy group at the end of a long-chain alkyl group, 1,2-
Epoxydecane, 1,2-epoxydodecane, 1,2-
Epoxy octadecane, 1,2-epoxydocosane,
1,2-epoxy octacosane, long-chain epoxide such as 1,2-epoxide triacontane, n-hexyl glycidyl ether, phenyl glycidyl ether, 2-
Examples thereof include ethylhexyl glycidyl ether and glycidyl ether of higher alcohol having 8 to 22 carbon atoms, but the present invention is not limited to these examples. These may be used alone or in combination of two or more.

The addition reaction of the epoxide (B) to the ethylene oxide-added polyether compound is carried out by adding ethylene oxide or the like to obtain an ethylene oxide-added polyether compound, for example, 100 to 18
The reaction can be carried out at 0 ° C. by a conventional method such as a method of reacting by adding the epoxide (B) in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate.

The proportion of the epoxide (B) used with respect to the ethylene oxide-added polyether compound is 0.4 to 10 mol, preferably 1 to 8 mol of the epoxide (B) with respect to one hydroxyl group of the ethylene oxide-added polyether compound. When the use ratio is less than 0.4 mol, the fragrance cleaner composition for flush toilets has a large solubility and cannot be improved in sustained dissolution and sustainability. Aroma cleaner composition for water flush toilets, because the water-soluble property deteriorates, the molded body collapses in water, and the shape remains indefinitely insoluble in water, or components that are insoluble in water are generated. It is difficult to get things.

The above-mentioned polyether compound is usually a solid compound that dissolves in water over a long period of time, and can be suitably used as a base for an aroma cleaner composition for flush toilets.

The polyether compounds of the present invention may be used alone or in combination of two or more, and when they are used in combination, the ratio is not particularly limited.

The blending ratio of the above polyether compound in the fragrance detergent composition for flush toilets is 40 to 85% (% by weight, the same applies hereinafter), preferably 50 to 75%. When the blending ratio is less than 40%, the sustained solubility and sustainability are not sufficiently exhibited, and when the blending ratio exceeds 85%, the improvement of the effect by the polyether compound is hardly recognized. .

In the fragrance cleaner composition for flush toilets of the present invention, a colorant (component (B)) is used as a pigment component for giving a refreshing feeling of flow.

Typical examples of the colorant include blue to green dyes and pigments, and specific examples thereof include Blue No. 1, Blue No. 2, Blue No. 202 and Green No. 3. To be

The proportion of the colorant in the fragrance detergent composition for flush toilets is 1 to 25%, preferably 2 to
It may be appropriately determined within the range of 20% depending on the type of colorant.
When the blending ratio is less than 1%, the color of the eluate is insufficient and the refreshing feeling and hygiene are not expressed. When the blending ratio exceeds 25%, the coloration is poor. It becomes too excessive and rather gives discomfort.

A perfume (component (C)) is used in the fragrance cleaner composition for flush toilets of the present invention.

The above-mentioned fragrance is not particularly limited, and those commonly used can be used.

Specific examples of the fragrance include isobornyl acetate, menthanyl acetate, frenchyl acetate, borneol, menthol, camphor, terpineol,
Examples include essential oils, pine extracts, terpinolenes, paradichlorobenzene, rose, lemon, jasmine, and bouquet flavors.

The mixing ratio of the fragrance in the fragrance cleaner composition for flush toilets is 1 to 30%, preferably 5 to 25%.
Within the range, it may be appropriately determined depending on the type of fragrance and the intensity of scent. When the blending ratio is less than 1%, the scent is too weak. On the other hand, if the blending ratio exceeds 30%, the heat resistance of the fragrance detergent composition for flush toilets may decrease, and the shape may be lost during storage.

In the fragrance cleansing composition for flush toilets of the present invention, anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, alkane sulfonates and the like; Nonionic surfactants such as oxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, fatty acid alkanolamides; emulsifying solubilizers of oily ingredients; various fungicides; various chelating agents; increasing amounts of sodium sulfate, potassium sulfate, glucose, etc. Agents; deodorizing components such as malic acid and glyoxal; additives such as silicone oil and the like can be added within a range that does not impair the object of the present invention.

The method for molding the fragrance cleaner composition for flush toilets of the present invention is not particularly limited, but one example thereof is, for example, heating and melting the base material and mixing with other components while stirring. Then, after gradually cooling to near the freezing point of the base, injecting it into the molding die and cooling and solidifying, after making the base and other compounding ingredients into fine powder and evenly mixing, compression molding, etc. Can be given.

Next, the fragrance cleaner composition for flush toilet of the present invention will be explained in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1 In a stainless steel autoclave, grade 1, grade 2 and grade 3
10 parts by weight of polyethyleneimine having primary amino nitrogen atoms in a ratio of 1: 2: 1, respectively, and having the number of active hydrogens and the number average molecular weight shown in Table 1 (parts by weight, hereinafter the same)
After charging, the inside of the autoclave was replaced with nitrogen. Then, 137 parts of propylene oxide was added and the reaction was carried out at 120 ° C, and then 842 parts of ethylene oxide was added and the reaction was carried out at 130 ° C.
An addition polymerization reaction was conducted at ℃ to obtain an ethylene oxide addition polyether compound having a number average molecular weight of 110,000.

Further, a mixed alkylene oxide having an average molecular weight of 196 obtained by mixing 1,2-epoxydodecane and 1,2-epoxytetradecane thereto (hereinafter referred to as AOE-
93 parts (1.9 mol per 1 hydroxyl group of the ethylene oxide-added polyether compound) was added and reacted at 150 ° C. to obtain a solid polyether compound (polyether compound (1)) at room temperature.

Production Examples 2 to 7 Active hydrogen number, number average molecular weight, kind of epoxide (A) of polyethyleneimine having primary, secondary and tertiary aminonitrogen atoms in a ratio of 1: 2: 1 respectively. As shown in Table 1, the weight ratio of epoxide (A) to ethylene oxide, the type of epoxide (B), and the amount used,
In Production Example 5, among the two types of epoxides (A),
Propylene oxide was added first to carry out the addition reaction, butylene oxide was then added to carry out the addition reaction. In Production Example 6, propylene oxide was added first to carry out the addition reaction, and then AOE-1 was added. Then, in Production Example 7, a polyether compound was prepared in the same manner as in Production Example 1 except that two kinds of epoxides (A) were simultaneously added so as to obtain a random copolymer. (2) to (7) were obtained.

[0043]

[Table 1]

Production Example 8 In an autoclave made of stainless steel, 28 active hydrogens were contained in one molecule, and primary, secondary and tertiary amino nitrogens were respectively provided at a ratio of 1: 2: 1, and the number average was obtained. Molecular weight 1200
Polyethyleneimine (10 parts) and stearic acid (6.9 parts) were added, and then dehydration condensation reaction was performed at 160 ° C under a nitrogen stream to obtain a partially amidated polyethyleneimine (number average molecular weight).
1432, the average number of active hydrogen 25) was obtained. Next, after replacing the inside of the autoclave with nitrogen, propylene oxide was replaced with 24
Two parts were added and the addition polymerization reaction was carried out at 120 ° C. Further, 917 parts of ethylene oxide was added and the addition polymerization reaction was carried out at 130 ° C. to obtain an ethylene oxide addition polyether compound having a number average molecular weight of 140,000.

Further, a mixed alkylene oxide (AOE-2) having an average molecular weight of 250 obtained by mixing 1,2-epoxyhexadecane and 1,2-epoxyoctadecane with this
Of 105 parts (2 moles per 1 hydroxyl group of the ethylene oxide-added polyether compound) was added and reacted at 150 ° C.
A polyether compound (polyether compound (8)) which was solid at room temperature was obtained.

Comparative Production Example 1 Ethylenediamine 10 instead of 10 parts of polyethyleneimine
Was used in the same manner as in Production Example 1 except that 133 parts of propylene oxide and 2522 parts of ethylene oxide (propylene oxide / ethylene oxide 5/95 (weight ratio)) were used to obtain an ethylene oxide-added polyether having a number average molecular weight of 15,000. Then, an epoxide adduct of ethylenediamine (polyether compound (9)) was obtained in the same manner as in Production Example 1 except that 209 parts of AOE-1 (1.5 mol per 1 mol of hydroxyl group of ethylene oxide adducted polyether) was used.

Examples 1 to 10 The respective components were heated and melt-mixed at the blending ratios shown in Table 2,
30 g of each was poured into a cylindrical mold having a diameter of 3.5 cm, cooled and solidified to prepare a fragrance detergent composition for flush toilets (compositions (1) to (10)).

Comparative Examples 1 to 6 Comparative aroma cleaner compositions for flush toilets (comparative compositions (1) to (6)) were prepared at the compounding ratios shown in Table 2 in the same manner as in Examples 1 to 10 above. did.

[0049]

[Table 2]

Test Examples 1-14 and Comparative Test Examples 1-7 Fragrance cleaner compositions for flush toilets (Compositions (1)-(1
0), Comparative compositions (1) to (6)) were installed at the bottom of the low tank (water storage: 12 liters, TOTO S-670 manufactured by Totoki Kiki Co., Ltd.) of a flush toilet for household use. Maintain the temperature of water and infused water at 25 ° C or 5 ° C,
It is set to automatically flush (running water) once per hour, and the number of usable days, the absorbance of running water, the shape of the fragrance cleaner composition for flush toilets, the adhesiveness, the strength of the scent, and the insoluble matter The presence / absence of the substance was examined according to the following method. The results are shown in Table 3.

(Number of usable days) The running water in the toilet for every 24 flashes was diluted 100 times with water, and the absorbance (630 nm) of the diluted solution was measured with a spectrophotometer UV-26 manufactured by Shimadzu Corporation.
The measurement was performed using 5FW, and the number of days until the absorbance became zero was examined.

(Absorbance of running water) Every 10 days (240 flashes) from the start of flushing, the running water in the toilet bowl is collected and
It was diluted 0 times and the absorbance was measured in the same manner as above.

(Shape) The day after the start of flashing, 10 days later,
After 20 days and 30 days, visually inspect the shape of the flush toilet aroma cleaner composition in the low tank, if there is almost no change ○, the upper part of the flush toilet aroma cleaner composition is slightly rounded If it is open △, the shape changes,
When the diameter spreads over 10 cm, it was evaluated as x.

(Adhesiveness) On the next day, 10 days, 20 days, and 30 days after the start of flushing, the toilet fragrance cleansing composition in the low tank was visually observed to confirm that it adhered to the bottom and was initially installed. It was evaluated as having no movement and having no movement.

(Strength of fragrance) 10 days after the start of flash
After a day, 20 days and 30 days, the smell of running water is judged by the sense of smell, 5 when the fragrance is strong, 4 when it is strong, 3 when it is normal, 2 when it is weak, and 2 when it is weak. The case was evaluated as 1.

(Presence or absence of insoluble matter) The running water for measuring the absorbance of running water was visually observed and evaluated as "no" when no insoluble matter was observed and "when" an insoluble matter was observed.

[0057]

[Table 3]

As is clear from the results shown in Table 3,
The fragrance cleaner composition for flush toilets of the present invention has low solubility in water, and thus has a long usable day (life), has little influence of solubility due to water temperature, maintains average solubility and fragrance, Moreover, it can be seen that there is adhesion to the bottom of the raw tank, there is no movement due to running water, there is no change in shape and no insoluble matter is generated.

[0059]

EFFECTS OF THE INVENTION The fragrance cleaner composition for flush toilets of the present invention has excellent sustained-solubility in water and has appropriate sustainability of blending components, and can be suitably used as a fragrance cleaner.

[Procedure amendment]

[Submission date] May 27, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Test Examples 1-14 and Comparative Test Examples 1-7 Fragrance cleaner compositions for flush toilets (Compositions (1)-(1
0), Comparative compositions (1) to (6)) were installed in the bottom of the low tank (water storage: 11 liters, TOTO S-670 manufactured by Totoki Kiki Co., Ltd.) of a domestic flush toilet, and Maintain the temperature of water and infused water at 25 ° C or 5 ° C,
It is set to automatically flush (running water) once per hour, and the number of usable days, the absorbance of running water, the shape of the fragrance cleaner composition for flush toilets, the adhesiveness, the strength of the scent, and the insoluble matter The presence / absence of the substance was examined according to the following method. The results are shown in Table 3.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051] (Available days) was measured using a 24 times the absorbance of the flow water in the toilet bowl per flash (630 nm) by Shimadzu Corp. spectrophotometer UV-265FW, until the absorbance becomes zero I checked the number of days.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C11D 3:40 3:50) (72) Inventor Fukunobu Mayu 3-17, Ogaya, Otsu City, Shiga Prefecture 8-515 (72) Inventor Katsunori Takeda 19 Nishi-Shichijo Higashikubo-cho, Shimogyo-ku, Kyoto (72) Inventor Shinichi Hamabe 11 Enohoncho Kashihara, Nishikyo-ku, Kyoto (72) Inventor Miho Shibata 19-3 Mibubaba-cho, Nakagyo-ku, Kyoto Detomwan Nijo Jonan 301

Claims (2)

[Claims] 1. A polyethyleneimine having (A) (a) 10 to 200 active hydrogens, a branched structure containing primary, secondary and tertiary amino nitrogen, and a number average molecular weight of 400 to 10,000. Alternatively, the above-mentioned polyethyleneimine derivative having 10 to 200 active hydrogens, an epoxide having 3 to 40 carbon atoms and ethylene oxide in a weight ratio of epoxide having 3 to 40 carbon atoms /
An ethylene oxide-added polyether compound having a number average molecular weight of 5,000 to 600,000, which is obtained by an addition reaction of ethylene oxide at a ratio of 0/100 to 50/50, and (b) a carbon number for one hydroxyl group of the ethylene oxide-added polyether compound. Aroma for flush toilet comprising 40 to 85% by weight of polyether compound obtained by addition reaction of 0.4 to 10 mol of epoxide of 8 to 40, (B) 1 to 25% by weight of colorant, and (C) 1 to 30% by weight of fragrance Cleaning composition. 2. Polyethyleneimine contains 12 to 10 active hydrogen.
It has 0, primary, secondary, and tertiary amino nitrogen atoms, respectively, in a ratio of 1: 1 to 1: 2.5: 1, and has a number average molecular weight of 500 to 5000. Item 1
The fragrance cleaner composition for flush toilets as described above.