JPH083590A - Cleaning agent composition for hard surface - Google Patents

Abstract

PURPOSE:To obtain the composition capable of sufficiently cleaning not only a common stain but also an oil stain having a high degree of denaturation by adding a surfactant, a builder and water to a prescribed acetal derivative. CONSTITUTION:This cleaning agent composition for hard surface contains (A) an acetal derivative of formula I (R<1> and R<2> are independently each H, a 1-5C alkyl, alkynyl, etc.; A is a 2-4C alkylene; (n) is 0-10), (B) a surfactant, (C) a builder and (D) water. The component A is synthesized by acetalizing or ketalizing with an aldehyde or a ketone with a glycerol in the presence of an acid catalyst by a scheme of formula II. The cleaning agent composition for hard surface suitable for a cleaning agent for kitchens is obtained.

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 an oil produced when edible oil scattered during cooking adheres to a hard surface such as a tile or enamel around a kitchen. TECHNICAL FIELD The present invention relates to a hard surface cleaner composition capable of effectively and safely removing and cleaning dirt and the like.

[0002]

2. Description of the Related Art Buses,
In kitchens, living rooms, etc., stubborn oil stains such as fats and oils are generated, but household detergents that wash these stains usually contain a surfactant, a solvent and an alkaline agent, Here, the solvent plays a very important role especially for cleaning the oil stains.

As a detergent containing such a solvent, conventionally, a household detergent containing a solvent such as ethylene propylene glycol monobutyl ether or butyl propylene glycol as an essential component has been known as an excellent detergent against oil stains. ing.

The above-mentioned detergents containing ethylene propylene glycol monobutyl ether or butyl propylene glycol, various surfactants and alkaline agents as basic components have relatively strong detergency against ordinary stains,
When it was attempted to effectively remove stains with less labor, the detergency was not sufficient, and in particular, the detergency against oil stains with a large degree of modification was not sufficient. Therefore, there has been a demand for a detergent composition capable of sufficiently cleaning oil stains having a large degree of modification.

[0005]

Under such circumstances, the present inventor has conducted diligent studies, and as a result, found that a detergent composition containing an acetal derivative having a specific structure has not only ordinary stains but also a modification degree. The present invention has been completed by finding that even large oil stains can be easily washed to a satisfactory level.

That is, the present invention provides the following component (a),
(B), (c) and (d): (a) an acetal derivative represented by the following formula (1),

[0007]

Embedded image

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl or alkenyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted by an alkyl group, A is an alkylene group having 2 to 4 carbon atoms,
n shows the number of 0-10. The present invention provides a hard surface cleaner composition containing (b) a surfactant, (c) a builder, and (d) water.

The acetal derivative of the component (a) used in the present invention is represented by the above formula (1). The alkyl group or alkenyl group represented by R ¹ and R ² in the formula (1) is a direct group. It may be linear, branched or cyclic, and preferably R ¹ and / or R ² has 1 to 5 carbon atoms and the total carbon number of R ¹ and R ² is 2 to 2 from the viewpoint of detergency.
5 is an alkyl group. Here, as the alkyl having 1 to 5 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, s
Examples thereof include an ec-butyl group and an n-pentyl group.

Examples of the phenyl group which may be substituted with an alkyl group include a phenyl group and a p-methylphenyl group. Of these, a phenyl group is particularly preferable. A more preferable combination of R ¹ and R ^2, when both R ¹ and R ² is an alkyl group having a total carbon number is 2 to 5 and R ¹ and R ² to 4 carbon atoms; R ¹ Is a hydrogen atom and R ² is an alkyl group having 1 to 5 carbon atoms or a phenyl group.

A is preferably a linear or branched alkylene group having 2 to 3 carbon atoms, that is, ethylene, propylene and trimethylene. Further, n is an average value, and particularly preferably 2-5.

Specific examples of the component (a) include the following formula (2) in which R ¹ / R ² is a methyl group / isobutyl group, a propyl group / hydrogen atom, a phenyl group / hydrogen atom, a pentyl group / hydrogen atom, Examples thereof include those having a methyl group / ethyl group, and it is particularly preferable to use those having 2 to 5 moles of EO (CH ₂ CH ₂ O) added thereto.

[0013]

Embedded image

The component (a) is acetalized or ketalized with an aldehyde or ketone (3) having a group corresponding to R ¹ and R ² and a glycerin (4) under an acid catalyst according to the following formula. It can be easily obtained by the method of conversion.

[0015]

[Chemical 4]

(Wherein R ¹ , R ² , A and n are the same as above)

The acid catalyst used in this reaction is PTS.
(P-toluenesulfonic acid), hydrochloric acid, and sulfuric acid may be mentioned. The reaction is 2 to 6 at 36 to 80 ° C. in a catalyst such as PTS.
It is preferable to do it for an hour.

The content of the above component (a) is preferably 0.1 to 50% by weight (hereinafter simply referred to as "%") in the total amount of the composition of the present invention, particularly preferably 1 to 20%, and further preferably. Is 5 to 15%. The content of component (a) is 0.1
If it is less than 50%, the detergent composition may not be able to exhibit high detergency, and if it exceeds 50%, the composition becomes aqueous and thus lacks stability.

The mechanism by which the acetal derivative (1) exhibits a high detergency against oil stains has not yet been clarified, but the acetal derivative (1) has a 1,3-dioxolane skeleton in its structure, It has a large penetrating effect on oils and fats, and as a result, it can be removed like strongly modified oil stains.
It is presumed that it shows an effective removal / cleaning ability for dirt that is extremely difficult to clean.

The surfactant used as the component (b) in the present invention is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. The activators can be used alone or in combination.

In the present invention, it is preferable to use a nonionic surfactant, such as polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkyl. Or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, alkylene oxide-added alkyl group- or alkenyl group-containing nonionic surfactant mixtures, sucrose fatty acid esters, fatty acid glycerin monoesters, higher fatty acid alkanolamides, amine oxides Examples thereof include ethylene oxide condensation type surfactants and alkyl glycosides represented by the following general formula (5).

[0022]

[Chemical 5] R ³ (OR ⁴ ) _x G _y (5)

(In the formula, R ³ represents a linear or branched alkyl group having 8 to 18 carbon atoms, or an alkenyl group or an alkylphenyl group, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, G represents a residue derived from a reducing sugar having 5 to 7 carbon atoms such as glucose, and x (average value) of the alkyl glycosides is 0 to 5 and y (average value) is 1 to 10. )

Among these, polyoxyethylene alkyl or alkenyl ethers, higher fatty acid alkanolamides and alkyl glycosides are particularly preferable, and specific examples thereof include polyoxyethylene (p = 12) lauryl ether, dodecyl maltoside and coconut. Examples thereof include fatty acid diethanolamide. These nonionic surfactants can be used alone or in combination of two or more.

Examples of the builder of the component (c) used in the present invention include alkanolamines such as mono-, di- or trialkanolamines and ammonia. Of these, monoethanolamine and diethanolamine are preferred from the viewpoint of detergency. preferable. These amine compounds may be used either individually or in combination of two or more.

The content of the component (b) and the component (c) in the composition of the present invention is 0.01 in the total amount of the composition.
The content of component (b) is preferably 0.1 to 20% from the viewpoint of the balance between skin irritation and detergency.
%, And component (c) is 0.01 to 20%. From the viewpoint of stability in water system, it is particularly preferably 0.05 to 10%.

The total amount of the above components (b) and (c) is preferably 0.01 to 70%, more preferably 0.05 to 50% from the viewpoint of cleaning effect.

The water of the component (d) used in the present invention is basically the balance with respect to the total amount of the components (a), (b) and (c) blended so as to preferably have the above content. When other components are added to the composition of the present invention, it means the balance with respect to the total amount including them,
Specifically, it is preferably 0.1 to 70%, particularly preferably 0.1 to 50%.

The composition of the present invention contains a low-temperature stabilizer, a viscosity modifier, and a low-temperature stabilizer, if necessary, as long as the desired performance is not impaired.
Arbitrary ingredients such as fragrances, pigments, preservatives, antioxidants and thickeners can be added.

Examples of the low temperature stabilizer include lower alcohols such as ethyl alcohol; lower glycols such as ethylene glycol; lower alkylbenzene sulfonates such as benzene sulfonate and toluene sulfonate.

As the viscosity modifier, a smectite type clay mineral containing montmorillonite, hectorite, vermiculite, attapulgite, sepiolact, and a mixture thereof known as expansive clay minerals; sodium polyacrylate, a cross-linking agent poly Acrylic homopolymers or copolymers such as polyacrylic acid alkyl esters; polyvinyl alcohol,
Examples thereof include hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, and maleic anhydride polymer.

The hard surface cleaner composition of the present invention is prepared, for example, as an aqueous solution by adding the above-mentioned optional components to the above-mentioned essential components (a) to (d), if necessary, according to a conventional method. You can

[0033]

Industrial Applicability The detergent composition for hard surfaces of the present invention has a significantly improved detergency for oil stains, especially modified oil stains, as compared with conventional detergents, and has a high practical value. Suitable for use as a kitchen cleaner.

[0034]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Prior to the description of the examples, synthesis examples of the acetal derivative of the component (a) used in the present invention will be described.

Synthesis Example 1 2-Methyl-2-isobutyl-synthesized from methyl isobutyl ketone and glycerin in a reaction tank (3.5 liters)
1,3-dioxolane-4-methanol 400.6 g
(2.299 mol), KOH 1.29 g (0.022
99 mol) and charged at 100 ° C and 30 Torr for 20
After dehydration for 30 minutes with stirring at 0 rpm, 203 g (4.5082 mol) of ethylene oxide (EO) was introduced over 50 minutes at 150 ° C so that the pressure did not exceed 3.5 atm, and further at 150 ° C for 50 minutes. Let react for minutes.
Next, the reaction solution was cooled to 70 ° C., and 162.31 g of a crude acetal derivative to which 2 mol of EO was added (n = 2 in the above formula (1)) was extracted. At this time, 4 in the reaction tank
42.58 g of reaction liquid remained.

Kyoward 600S (Kyowa Chemical Industry Co., Ltd.) 2.77 was added to the crude acetal derivative obtained above.
After adding g, dehydration was performed while bubbling nitrogen at 250 Torr and 100 ° C. for 1 hour to remove the KOH catalyst by adsorption. Next, a PTFE membrane filter (0.2
(150 μm) to obtain a purified product (I) of an acetal derivative (R ¹ ═CH ₃ , R ² ═iC ₄ H ₉ , n = 2 in the above formula (1)) (150.94 g). N of purified product (I)
The results of MR analysis and IR analysis are shown below.

[0037]

[Table 1]

IR (NEAT, cm ^-1 ): 3472 (OH expansion and contraction), 2960,
2876 (CH expansion / contraction), 1470, 1378 (CH deflection), 1294, 1246 (OH
Deflection), 1186, 1140, 1120, 1070 (COCOC expansion / contraction), 1096
(COC expansion / contraction), 1050 (CO expansion / contraction)

Synthesis Example 2 The reaction liquid 44 remaining in the reaction vessel in Synthesis Example 1
To 2.58 g, 148 g (3.3597 mol) of ethylene oxide was introduced over 35 minutes so that the pressure did not exceed 3.7 at 150 ° C., and the mixture was further reacted at 150 ° C. for 45 minutes. The reaction was then cooled to 80 ° C. and EO was adjusted to 4
179.27 g of the mole-added crude acetal derivative (n = 4 in the above formula (1)) was extracted. At this time, 411.63 g of the reaction liquid remained in the reaction tank. Next, 2.29 g of Kyoward 600S was added to the crude acetal derivative obtained above, and a purification operation was performed in the same manner as described above to obtain an acetal derivative (in the formula (1), R ¹ = CH ₃ , R ² = Purified product (II) of iC ₄ H ₉ , n = 4)
174.06g was obtained. The NMR analysis and IR analysis results of the purified product (II) are shown below.

[0040]

[Table 2]

IR (NEAT, cm ^-1 ): 3464 (OH expansion and contraction), 2960,
2876 (CH expansion / contraction), 1468, 1376 (CH deflection), 1294, 1250 (OH
Deflection), 1186, 1140, 1120 (COCOC expansion / contraction), 1100 (COC
Expansion / contraction), 1050 (CO expansion / contraction)

Synthetic Example 3 The reaction liquid 41 remaining in the reaction vessel in Synthetic Example 2
To 1.63 g, 155 g (3.5186 mol) of ethylene oxide was introduced over a period of 40 minutes so that the pressure did not exceed 3.7 at 150 ° C., and the reaction was further performed at 150 ° C. for 30 minutes. The reaction is then cooled to 80 ° C. and the EO is 7
(In the above formula (1), R ¹ = CH ₃ , R ²
= IC ₄ H ₉ , n = 7) as a crude acetal derivative of 563.6.
g was taken out. By adding 5.23 g of KYOWARD 600S to this crude acetal derivative and performing a purification operation in the same manner as above, 556.31 g of a purified product (III) of the acetal derivative (n = 7 in the above formula (1)) was obtained. . The results of NMR analysis and IR analysis of the purified product (III) are shown below.

[0043]

[Table 3]

IR (NEAT, cm ^-1 ): 3392 (OH expansion and contraction), 2960,
2876 (CH expansion / contraction), 1470, 1354 (CH deflection), 1296, 1250 (OH
Deflection), 1186, 1140, 1120 (COCOC expansion / contraction), 1100 (COC
Expansion / contraction), 1050 (CO expansion / contraction)

Purity and OHV of the purified acetal derivative (I), (II) and (III) obtained above
(Hydroxyl value) was measured. Also, the solubility in water (g
/ 100 g water) is 0.1 to 0.1% acetal derivative (I).
5, (II) and (III) were 20. The results are shown in Table 4.

[0046]

[Table 4]

Examples 1 to 8 and Comparative Example 1 Cleaning agent compositions having the compositions shown in Tables 5 to 7 were prepared, and the following tests were carried out on these cleaning agent compositions. The results are shown in Tables 5-7.

[Detergency Test] First, tempura oil was uniformly applied to an iron plate and baked at a temperature of 180 ° C. for 30 minutes to form an almost completely dried oil film to prepare a model contaminated plate. Next, this model contaminated plate was fixed, the cleaning composition was dropped vertically on it, left for 40 seconds, and the floating dirt was lightly rubbed with absorbent cotton to remove it, and the degree of cleaning (cleaning power) was as follows. It was evaluated with the naked eye in accordance with the evaluation standard.

⊚: Complete stain removal. ◯: About 80% stain removal. □: About 50% stain removal. Δ: About 20% stain removal. ×: Almost no stain is removed.

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

From the results shown in Table 5, Table 6 and Table 7, the cleaning composition of the present invention containing the components (a), (b), (c) and (d) is the cleaning composition of Comparative Example. It can be seen that it has a good detergency as compared with.

Front Page Continuation (72) Inventor Tsukuda Ikkun No. 203 Kawamata Heights, 1545-8 Shimoguricho, Utsunomiya City, Tochigi Prefecture (72) Inventor Shoji Nakagawa 1-3-2 Nishikojiri, Wakayama City, Wakayama Prefecture

Claims (4)

[Claims] 1. The following components (a), (b), (c) and (d): (a) an acetal derivative represented by the following formula (1): (In the formula, R ¹ and R ² may be the same or different,
A hydrogen atom, an alkyl group or an alkenyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted by an alkyl group is shown, A is an alkylene group having 2 to 4 carbon atoms, and n is 0 to 10
Indicates the number of. (B) A surfactant, (c) builder, and (d) water are contained, The hard surface cleaner composition characterized by the above-mentioned. 2. In the general formula (1), R ¹ and R
² has 1 to 4 carbon atoms and the total carbon number of R ¹ and R ² is 2
The cleaning composition for hard surfaces according to claim 1, wherein n is a number of 2 to 5 in an alkyl group of 5 to 5. 3. The content of the component (a) is 0.01-5.
0% by weight, the content of the component (b) is 0.01 to 50% by weight, the content of the component (c) is 0.01 to 50% by weight, and the balance is water, and the component (b) and the component ( The cleaning composition for hard surfaces according to claim 1 or 2, wherein the total content with c) is 0.1 to 70% by weight. 4. The hard surface cleaner composition according to claim 1, wherein the composition is a modified oil stain cleaner composition.