JP3238435B2 - Aromatic detergent composition for flush toilet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic detergent composition for flush toilets. More specifically, the present invention relates to an aromatic detergent composition for flush toilets having a long dissolution and disappearance time of the molded article.

[0002]

2. Description of the Related Art Fragrance detergents for flush toilets are generally solid, and are stored in a container or directly put into a flush tank of a flush toilet, or attached to a hand washing section of a flush tank. By gradually dissolving or dispersing the composition in the stored water in the tank, washing the toilet bowl and the like together with the running water at the time of washing, and scenting the fragrance, it is used as an agent for keeping the inside of the toilet refreshing. Have been.

[0003] The above-mentioned fragrance detergent for flush toilets contains a base in addition to the fragrance component and the cleaning component.
This base not only functions as a binder to solidify the fragrance and cleaning components, but also controls the dissolution rate of the blended components in running water and water to maintain proper fragrance and detergency for a proper period of time. Has a role.

[0004] Such bases include polyethylene glycol, those obtained by substituting a hydroxyl group at one or both terminals of polyethylene glycol with a hydrophobic group such as an alkyl group to form ethers or esters (hereinafter referred to as polyethylene glycol type), and propylene. Oxides having both hydrogen atoms at the both ends comprising only oxide and ethylene oxide (hereinafter referred to as copolymer type) are used (JP-A-51-39705, JP-A-53-31709, JP-A-55-131098, and JP-A-55-131098). Five
No. 7-179298).

[0005] However, the bases of these conventional fragrance cleaners for flush toilets have the following problems.

[0006] Polyethylene glycol has a fundamental problem in that the water solubility is too large and thus the durability is poor, and the water solubility depends on the water temperature. That is, if the water solubility is too large, the elution rate of the compounding components such as the aromatic component and the cleaning component increases, and the effect is lost in a short time. Therefore, in order to reduce the elution rate, if the molecular weight is increased, the elution rate can be reduced to some extent, but the production efficiency deteriorates because it takes a long time to increase the molecular weight, It will be expensive.

[0007] The polyethylene glycol type has a long lasting property, but has a low water solubility, and when used as a base for a fragrance cleaner for flush toilet, toilet flush water may become turbid.

[0008] Further, the copolymer type is insufficient in spite of having better durability than polyethylene glycol.

[0009]

Therefore, in view of the above-mentioned prior art, the present inventors have found that the dissolution and elimination time of a compound such as an aromatic component or a washing component is long, that is, water washing which is excellent in sustained release of the compound. As a result of intensive studies to develop a fragrance detergent composition for toilets, a fragrance detergent composition excellent in such properties was finally found, and the present invention was completed.

[0010]

Means for Solving the Problems That is, the present invention relates to (A)
General formula (I):

[0011]

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Wherein R ¹ comprises an organic compound having 1 to 8 active hydrogen atoms, 0 to 98% by weight of an epoxide having 3 carbon atoms and 2 to 100% by weight of an epoxide having 4 to 40 carbon atoms. Weight average molecular weight 500 obtained by polymerizing epoxide
Polymer residues ~12000, R ² is at least one hydrogen atom and a methyl group, at least 75 mole percent hydrogen atom of R ^2, p is an integer of 1 to 8, n represents

[0013]

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A polyether compound obtained by ring-opening polymerization of a compound represented by the formula (1) and an epoxide having 4 to 40 carbon atoms; and (B) a compound represented by the above general formula (I) The present invention relates to a fragrance detergent composition for flush toilets, comprising as a base at least one of ester compounds with fatty acids of the formulas 8 to 30.

[0015]

Action and Examples As described above, the aromatic detergent composition for flush toilets of the present invention comprises (A) the general formula (I):

[0016]

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(Wherein R ¹ comprises an organic compound having 1 to 8 active hydrogen atoms, 0 to 98% by weight of an epoxide having 3 carbon atoms and 2 to 100% by weight of an epoxide having 4 to 40 carbon atoms) residues having a weight average molecular weight from 500 to 12,000, which is E by polymerizing epoxides, R ² is at least one hydrogen atom and a methyl group, the R ² at least
75 mol% is a hydrogen atom, p is an integer of 1 to 8, n is

[0018]

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A polyether compound obtained by ring-opening polymerization of a compound represented by the formula (1) and an epoxide having 4 to 40 carbon atoms, and (B) a compound represented by the general formula (I) It contains at least one of ester compounds with fatty acids of several 8 to 30 as a base.

In the organic compound having 1 to 8 active hydrogen atoms represented by the general formula (I), the number of active hydrogen atoms is 1 to 8, preferably 1 to 4. Examples of the organic compound having 1 to 8 active hydrogen atoms include higher aliphatic alcohols, alkylphenols having a linear or branched alkyl group, (poly) ethylene glycol, (poly) propylene glycol,
(Poly) butylene glycol, bisphenol A, glycerin, trimethylolpropane, pentaerythritol, sorbitol, aliphatic amines and the like,
The present invention is not limited to only such examples. Among these organic compounds having 1 to 8 active hydrogen atoms, higher aliphatic alcohols, alkylphenols, (poly) ethylene glycol, (poly) propylene glycol, bisphenol A, etc. are easily available and have a high temperature. Since it has excellent quality stability at the time, it can be particularly preferably used.

The epoxide having 3 carbon atoms is, specifically,
1,2-epoxypropane.

The epoxide having 4 to 40 carbon atoms includes
For example, alkylene oxide, α-olefin epoxide, styrene oxide and the like can be mentioned, but the present invention is not limited only to such examples. The epoxide preferably has 15 to 35 carbon atoms, especially 20 to 30 carbon atoms, from the viewpoint of water solubility.

The epoxide used in the present invention is composed of the epoxide having 3 carbon atoms and the epoxide having 4 to 40 carbon atoms. When the ratio of the epoxide having 3 carbon atoms exceeds 98% by weight, When the proportion of the epoxide having 4 to 40 carbon atoms is less than 2% by weight, the dissolution rate of the obtained base in water increases and the sustainability decreases. Is 0
The content of the epoxide having 4 to 40 carbon atoms is adjusted to be 2 to 100% by weight. In the present invention, in order to impart more appropriate solubility, the ratio of the epoxide having 3 carbon atoms is 40 to 98% by weight,
The ratio of the epoxide having 4 to 40 carbon atoms is preferably 2 to 60% by weight.

By polymerizing the organic compound having 1 to 8 active hydrogen atoms and the epoxide,
Although a polymer having a weight average molecular weight of 500 to 12000 is obtained, the molar ratio of the organic compound having 1 to 8 active hydrogen atoms to the epoxide is not particularly limited, and may be appropriately adjusted according to the desired water solubility. I just need.

When the weight-average molecular weight of the polymer is less than 500, the dissolution rate of the obtained base in water becomes too high, and when it exceeds 12000, the viscosity becomes too high. In the present invention, it is difficult to ethoxylate and propoxylate the polymer.
500-12000, preferably 1000-5000. The polymer contains active hydrogen derived from the above 1 to 8 active hydrogen atoms from an organic compound, and the portion excluding such active hydrogen is referred to as a residue of the polymer in this specification.

In the general formula (I), the formula (II):

[0027]

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R ^{2 in the} group represented by is at least one of a hydrogen atom and a methyl group, p is an integer of 1 to 8,
Is

[0029]

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Is an integer that satisfies

R ² has at least 75 mol% a hydrogen atom. When the proportion of hydrogen atoms is smaller than 75 mol%, the melting point of the obtained base material becomes too low, and the formability of the base material becomes poor.

In the compound represented by the general formula (I),

[0033]

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When the ratio is less than 5/95, the dissolution rate of the obtained base in water becomes too high, so that the sustainability of the components becomes small. Since the melting point of the base material becomes low and the moldability of the base material becomes poor, n is selected so as to satisfy such a weight ratio. The weight ratio is preferably from 5/95 to 30/70.

The compound represented by the general formula (I) can be easily synthesized by a known method, for example, the following method.

First, a basic catalyst such as caustic soda is added to the organic compound having 1 to 8 active hydrogen atoms, the temperature is increased to about 100 ° C. by replacing with nitrogen gas, and a predetermined amount of the epoxide is added. To react. Then, a compound represented by the above general formula (I) is obtained by subjecting at least one of ethylene oxide and propylene oxide to a predetermined amount in a polymerization reaction with the obtained product. The weight average molecular weight of such a compound is preferably 5,000 to 50,000, more preferably 10,000 to 20,000 in consideration of the solubility of the obtained base in water and moldability in a detergent.

The compound represented by the general formula (I) is a useful compound which can be used as a base in a fragrance detergent composition. In the present invention, a polyether compound and an ester as shown below are used. Used as a compound. These compounds have a function of dissolving the obtained base in water at a lower rate than that of the compound represented by the above general formula (I) and increasing the durability of the components.

The polyether compound has the general formula
It can be obtained by ring-opening polymerization of the compound represented by (I) and an epoxide having 4 to 40 carbon atoms.

Specific examples of the epoxide having 4 to 40 carbon atoms include alkylene oxide, α-olefin oxide, styrene oxide and the like, but the present invention is not limited to these examples. In addition,
The carbon number of such an epoxide is 15 to 35 from the viewpoint of water solubility,
Preferably, it is 20 to 30.

The amount of the epoxide having 4 to 40 carbon atoms to be subjected to the reaction may be appropriately adjusted in consideration of the water solubility of the obtained aromatic detergent, disintegration in water, and shape stability at high temperatures. Good.

The method of subjecting the compound represented by the general formula (I) to ring-opening polymerization with an epoxide having 4 to 40 carbon atoms is not particularly limited, and any method generally used may be used.

If the polymerization average molecular weight of the polyether compound is too large, the viscosity becomes too large and the production efficiency of the aromatic detergent becomes poor, and if it is too small, the melting point becomes too low. As the aromatic detergent obtained by being too low will deform at high temperatures,
It is preferably about 10,000 to 22,000.

The ester compound is obtained by reacting the compound represented by the general formula (I) with a fatty acid having 8 to 30 carbon atoms.

Specific examples of the fatty acid having 8 to 30 carbon atoms include capsolic acid, undecanoic acid, lauric acid, and the like.
Examples include myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, cerotic acid, melicic acid, their acid halides, acid anhydrides, and the like, but the present invention is not limited only to these examples.

The amount of the fatty acid having 8 to 30 carbon atoms to be reacted is usually the amount of the OH of the compound represented by the general formula (I).
A stoichiometric amount of COOH group per equivalent of group, preferably 1 to
Adjusted to 1.4 equivalents.

The method of the esterification reaction between the compound represented by the general formula (I) and a fatty acid having 8 to 30 carbon atoms includes:
For example, there is a method of esterification under ordinary heating under reduced pressure, but the present invention is not limited to such a method.

The polyether compound and the ester compound are both used in the fragrance detergent composition of the present invention.
These compounds are used as a base, and these compounds are usually used alone or in combination of two or more.

The amount of at least one of the above-mentioned polyether compounds and ester compounds to be added to the aroma detergent composition as a base varies depending on the kind of the ingredients, the form of the obtained detergent, and the like. However, it is usually adjusted so as to be contained at 50 to 75% by weight in the aroma detergent composition.

The compounding ingredients to be mixed in the above-mentioned fragrance detergent composition include, for example, fragrance ingredients typified by compounded flavors,
Deodorizing components such as malic acid and glyoxal, ether-type nonionic surfactants, α-olefin hydrocarbon compounds, alkyl ether sulfates and other cleaning components commonly used in aromatic detergents, such as toilets Various coloring agents capable of imparting a feeling of cleanliness to running water, emulsifying solubilizers for oily components, various disinfectants, various chelating agents, extenders such as sodium sulfate and glucose, and solubility modifiers such as polyethylene glycol and its derivatives. Additives and the like can be mentioned, the blending ratio of these is appropriately determined according to the form of the obtained aromatic detergent and the like.
For example, 1 to 30% by weight of an aromatic component or a deodorant component, 3 to 50% by weight of a cleaning component, and 0 to 50% by weight of other additives based on the aromatic detergent composition.

By using at least one of the above-mentioned polyether compounds and ester compounds as a base and mixing it with the above-mentioned components, an aromatic detergent composition for flush toilets of the present invention can be obtained.

The method for forming an aromatic detergent using the aromatic detergent composition of the present invention is not particularly limited. One example is, for example, a method in which a base is heated and melted and then mixed with stirring. , Then slowly cooled to around the solidification point of the base, poured into a mold, cooled and solidified, a method of uniformly mixing the base and compounded components into fine powders, and then compression molding And so on.

Next, the fragrance detergent composition for flush toilets of the present invention will be described in more detail with reference to Examples.
The present invention is not limited to only such embodiments.

Production Example 1 (Production of polyether compound A) 1 part (part by weight, hereinafter the same) of propylene glycol was added to an autoclave, and KOH was used as a basic catalyst.
After adding 0.05 part, the inside of the autoclave was replaced with nitrogen gas. Next, 13 parts of butylene oxide were added, and 10 parts of butylene oxide were added.
The temperature was raised to 0 ° C. to complete the reaction. Next, 33 parts of propylene oxide was added for polymerization, and the weight average molecular weight of the obtained polymer was determined to be 2560.

Next, 185 parts of ethylene oxide were added into the autoclave, and the reaction was completed while maintaining the temperature at 130 ° C. When the content of R ¹ group in the general formula (I) contained in the obtained compound A was examined, it was 20% by weight.

Further, in the autoclave, a molecular weight of 380
1,2-epoxyalkane (α-olefin epoxide) 8
Was added and stirred at 130 ° C. to carry out ring-opening polymerization to obtain 240 parts of a polyether compound A having a weight average molecular weight of 12500.

Production Example 2 (Production of polyether compound B) 1 part of glycerin was added to an autoclave, and the inside thereof was replaced with nitrogen gas. Next, 1, with a molecular weight of 380
6 parts of 2-epoxyalkane (α-olefin epoxide) are added, the temperature is raised to 100 ° C., stirring is continued, and a mixture of 45 parts of propylene oxide and 5 parts of butylene oxide is added to maintain the temperature at 100 ° C. While continuing stirring, the reaction was completed. When the weight average molecular weight of the polymer was determined, it was 4,800.

Next, 250 parts of ethylene oxide was added into the autoclave, and stirring was continued while maintaining the temperature at 130 ° C. to obtain a compound B. When the content of R ¹ in the general formula (I) contained in the obtained compound B was examined in the same manner as in Production Example 1, it was 19% by weight.

Further, in the autoclave, a molecular weight of 200
1,2-epoxyalkane (α-olefin epoxide) 5
Was added, and ring-opening polymerization was carried out while stirring at 130 ° C.
There were obtained 312 parts of a polyether compound B having a weight average molecular weight of 23000.

Production Example 3 (Production of Ester Compound A) 307 parts of the compound B obtained in Production Example 2 was added into a nitrogen-substituted flask, and then palmitic acid chloride was added.
5 parts were added, and the mixture was stirred for 5 hours while maintaining the temperature at about 200 ° C. to carry out an esterification reaction to obtain an ester compound A.
312.5 copies.

EXPERIMENTAL EXAMPLE 1 Compound A, compound B, polyether compound A, polyether compound B and ester compound A obtained in Production Examples 1 to 3, polyethylene glycol, polyethylene glycol The solubility in water was examined using the ethylene oxide adduct of stearate and polypropylene glycol according to the following method. Table 1 shows the results.

(Solubility in Water) The base was about 16 mm in diameter,
It is molded into a columnar shape with a length of 700 mm, left standing in about 5 liters of water at 25 ° C., and visually observes the dissolution state of the molded article, and the time required for complete dissolution (time required for dissolution and disappearance A). Was measured.

Next, when the time A required for dissolution and disappearance is 1500 minutes or more, a molded product is prepared by adjusting the base so that polyethylene glycol having a molecular weight of 20,000 is contained at 50% by weight. The time required for the molded product to completely dissolve (time required for dissolution and disappearance B) was measured.

[0063]

[Table 1]

As is clear from the results shown in Table 1, the base used in the present invention has low solubility in water,
It can be seen that the composition can be suitably used for an aromatic detergent composition.

Example 1 Among the following components, the polyether compound A obtained in Production Example 1, which is the base, was heated and melted, and the remaining components were added and mixed with stirring, and gradually cooled to near the freezing point. After that, it was put into a molding die and solidified to prepare a flush toilet fragrance.

(Components) (parts by weight) Polyether compound A 65 Perfume 20 Cleaning component (polyoxyethylene sorbitan fatty acid ester) 5 Colorant 10 Example 2 Using polyether compound B obtained in Production Example 2, The mixture was mixed and solidified in the same manner as in Example 1 to produce an aromatic detergent for flush toilets.

(Components) (parts by weight) Polyether compound B 60 perfume 20 Cleaning component (polyoxyethylene sorbitan fatty acid ester) 5 Colorant 10 Neutral anhydrous sodium sulfate 5 Example 3 Ester compound obtained in Production Example 3 Example 1 using A
The mixture was mixed and solidified in the same manner as in the above to prepare an aromatic detergent for flush toilet.

(Components) (parts by weight) Ester compound A 65 Perfume 20 Cleaning component (polyoxyethylene sorbitan fatty acid ester) 5 Colorant 10 Comparative Example 1 In Example 1, polyethylene glycol having a molecular weight of 6000 was used as a base. A fragrance cleaner for flush toilet for comparison was prepared in the same manner as in Example 1 except that it was used.

Experimental Example 2 As shown in FIG. 1, a lid 3 having a water inlet opening 1 on the top and four water outlets 2 on the side and a cylindrical body 4 having a diameter of 40 mm and a height of 70 mm were formed. The container was filled with 50 g of each of the aromatic detergents 5 of Examples 1 to 3 and Comparative Example 1, and then cooled and solidified.

These containers were used as low tanks for home flush toilets (water storage: 12 liters, TO TOKI Kiki Co., Ltd.
TOS-670), and the number of times it could be used and the average absorbance (630 nm) of the running water in the toilet were measured using a spectrophotometer UV-265FW (Shimadzu Corporation). In addition, the temperature of the water in the low tank and the injection water was maintained at 30 ° C. or 5 ° C., and each was set to automatically flush (flow water) once an hour. The usable number of times means the number of times until the average absorbance of the running water in the toilet becomes zero under the above conditions. Table 2 shows the results.

[0071]

[Table 2]

As is clear from the results shown in Table 2, the base used in the present invention has low solubility in water,
Accordingly, an appropriate number of times of use and an average absorbance (630 nm) of running water in the toilet are obtained, and it can be seen that the composition can be suitably used for an aromatic cleaning composition.

[0073]

EFFECTS OF THE INVENTION The fragrance cleaning composition for flush toilets of the present invention has a moderately slower dissolution rate in water than a fragrance cleaning composition based on a polyethylene glycol type, and has an appropriate compounding component. It can be suitably used as a fragrance cleaner since it has a long lasting effect.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a container for filling an aromatic detergent for a flush toilet used in Experimental Example 2.

[Explanation of symbols]

 5 Aroma cleaner

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // C09K 3/00 110 C09K 3/00 110B (72) Inventor Junichi Matsumoto 2-29-29 Kinukawa, Otsu-shi, Shiga Prefecture (72) ) Inventor Miho Shibata 19-3 Mibu Babacho, Nakagyo-ku, Kyoto 30-1 Detom One Nijo-jojo Minami (56) References JP-A-3-124789 (JP, A) JP-A-57-179298 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 17/00 C11D 1/74 C11D 3/37 C09K 3/00 110

Claims (1)

(57) [Claims] (A) General formula (I): (Wherein R ¹ represents an organic compound having 1 to 8 active hydrogen atoms, an epoxide comprising 0 to 98% by weight of an epoxide having 3 carbon atoms and 2 to 100% by weight of an epoxide having 4 to 40 carbon atoms) The residue of a polymer having a weight average molecular weight of 500 to 12000 obtained by polymerization, R ² is at least one of a hydrogen atom and a methyl group, at least 75 mol% of R ² is a hydrogen atom, and p is 1 to 8 Integer, n is Weight average molecular weight of 50 represented by the following formula:
A polyether compound obtained by ring-opening polymerization of a compound of 00 to 50,000 and an epoxide of 4 to 40 carbon atoms; and (B) a compound represented by the above general formula (I) and a compound of 8 to 30 carbon atoms.
An aromatic detergent composition for flush toilets, comprising as a base at least one ester compound with a fatty acid.