JP3422457B2 - Higher alcohol concentrated neutral detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a higher alcohol-based concentrated neutral detergent composition which is excellent in transparency and stability and is economical in cost.

[0002]

2. Description of the Related Art Among neutral detergent compositions conventionally used as dishwashing detergents, those for commercial use have a surfactant component concentration adjusted to about 10 to 15% by weight (hereinafter abbreviated as "%"). The mainstream products were those filled with Ito cans (capacity 18 liters) and plastic containers. However, these Ito cans and plastic containers are expensive to dispose of, and a recycling system cannot be established. Bag-shaped containers called "paper packs" and "standing pouches" have been widely used not only for home use but also for business use.

Although the above-mentioned standing pouch is made of plastic, it is relatively easy to process because it is used in a small amount, and it is compact and space-saving for the user side. It is welcomed because of its convenience.

[0004]

However, since the pouch is a flexible bag, it is more difficult to fill the cleaning composition (liquid) than a can or a poly container, and the filling speed must be slow. . Therefore, by increasing the concentration of the surfactant component, productivity and cost reduction have been attempted. However, due to growing concern over environmental issues, the demand for natural products (higher alcohols) has increased. High-concentration surfactant components, gelation occurs due to the nonionic surfactant, which is the main component, and the transparency is lost, or the fluidity decreases at low temperatures. Then, there is a problem such as solidification. These phenomena are likely to occur especially when the concentration of the surfactant component is 40 to 60%.

On the other hand, in order to eliminate gelation and solidification, a large amount (10 to 20%) of solvent, for example, lower alcohol such as ethanol, propylene glycol, polyethylene glycol or the like is used. However, when a large amount of these solvents is blended, there are problems that a strong solvent odor is imparted to the product and that the viscosity becomes too low and the detergent is used too much. In addition, although some use of fragrances to mask solvent odors has been implemented, some users find that the cost is rather high and the odor of fragrances is a concern, so it is important to keep the solvent content low. It has become a challenge.

JP-A-6-240292 discloses a very high-concentration neutral detergent composition having a surfactant component concentration of 60% or more. Since the viscosity is adjusted by blending a relatively large amount and an amphoteric surfactant, the cost is high. Further, since the concentration of the surfactant is very high, it may be difficult to dissolve in water at a low temperature such as winter.

The present invention has been made in view of the above circumstances, and has a superior alcohol-based concentrated neutral detergent composition of excellent quality, which keeps the amount of solvent blended low and does not cause gelation or low-temperature solidification. The purpose is to provide.

[0008]

In order to achieve the above object, the invention according to claim 1 of the present invention comprises:
The surfactant component containing the component (C) as an essential component is contained at a concentration of 30 to 55% with respect to the entire composition, and the following components (D) and (E) are contained.
A higher alcohol-based concentrated neutral detergent composition having a composition viscosity at 400C of 400 to 1100 cps. (A) Polyoxyethylene alkyl obtained by combining 2 to 6 mol adduct of higher alcohol (x) 1 to 9% and 7 to 12 mol adduct of higher alcohol (y) 10 to 30%. Ether type nonionic surfactant 11-35%. (B) Alkyl sulfate ester salt, alkyl ether sulfate
Ester salts, alkane sulfonates and α-olefins
At least one selected from the group consisting of
4% to 10% of anionic surfactant. (C) 5-33% of fatty acid alkanolamide. (D) pH adjuster. (E) Solvent component 3 to 7 %.

The invention according to claim 2 of the present invention is
In the polyoxyethylene alkyl ether as the component (A), (x) and (y) are (x) :( y) = 9: 1.
A higher alcohol-based concentrated neutral detergent composition, which is combined in a weight ratio of 6 to 1:24, and is defined in Claim 3 of the present invention.
The invention according to (1) is a higher alcohol-based concentrated neutral detergent composition in which the anionic surfactant as the component (B) comprises at least one of an alkyl sulfate ester salt (p) and an alkyl ether sulfate ester salt (r).

Further, in the invention according to claim 4 of the present invention, the anionic surfactant of the component (B) comprises an alkyl sulfate ester salt (p) and an alkyl ether sulfate ester salt (r), and (p) And (r) becomes (p):
(R) = 1: 4 to 4: 1 is a higher alcohol-based concentrated neutral detergent composition combined in a weight ratio, and the invention according to claim 5 of the present invention provides pH adjustment of the component (D). The agent is a higher alcohol concentrated neutral detergent composition in which the agent is at least one acid selected from the group consisting of citric acid, boric acid and sulfuric acid.

That is, in the present invention, by using a special polyoxyethylene alkyl ether type nonionic surfactant as the component (A), the gelation phenomenon or the low temperature solidification phenomenon can be achieved while suppressing the compounding amount of the solvent to a low level. To eliminate
A transparent appearance is obtained by neutralizing with a pH adjuster which is the component (D), and a very stable quality is obtained despite the fact that the concentration of the surfactant component is set relatively high. It is equipped and easy to use. Further, since no expensive component material is used, the cost can be kept low.

Among the above-mentioned component (A), particularly, a 2 to 6 mol adduct of ethylene oxide with a higher alcohol (hereinafter abbreviated as "higher alcohol 2 to 6 EO"),
A combination of a higher alcohol ethylene oxide 7 to 12 mol adduct (hereinafter abbreviated as “higher alcohol 7 to 12 EO”) in a weight ratio of 9:16 to 1:24 is more excellent in the above effect.

Among the anionic surfactants as the component (B), those using at least one of the alkyl sulfate ester salt and the alkyl ether sulfate ester salt are excellent in cleaning performance and mild feeling to the hand. Among them, a combination of the alkyl sulfate ester salt and the alkyl ether sulfate ester salt in a weight ratio of 1: 4 to 4: 1 produces particularly excellent effects.

Further, among the pH adjusters of the above-mentioned component (D), those using at least one acid selected from the group consisting of citric acid, boric acid and sulfuric acid are particularly stable at low temperature and with time of pH. It has excellent stability.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described.

The polyoxyethylene alkyl ether type surfactant used as the component (A) of the present invention is a higher alcohol 2 to 6 EO (x) and a higher alcohol 7-1.
It is a combination of 2EO (y).

Examples of the higher alcohols 2 to 6EO (x) include ethylene oxide 2 to 6 mole adducts of higher alcohols having 8 to 18 carbon atoms, and among them, ethylene oxide of higher alcohols having 10 to 14 carbon atoms. 2 to
A 3 molar adduct is preferred. This compound is contained in the range of 1 to 9% with respect to the entire composition, but by setting the content to 3 to 7%, it is possible to obtain particularly excellent viscosity characteristics, low temperature stability and transparency. Obtainable.

Further, the above-mentioned higher alcohol 7-12EO
Examples of (y) include ethylene oxide 7 to 12 mol adducts of higher alcohols having 10 to 18 carbon atoms, and among them, ethylene oxide 8 to 10 mol adducts of higher alcohols having 10 to 14 carbon atoms are preferable. is there. This compound is contained in the range of 10 to 30% with respect to the entire composition, but by setting the content to 13 to 28%, it is possible to obtain particularly excellent viscosity characteristics, low temperature stability and transparency. Obtainable.

By using the above two kinds of higher alcohol ethylene oxide adducts (x) and (y) in combination, the gelation phenomenon and the low temperature solidification phenomenon of the high-concentration surfactant component can be eliminated. Moreover, the compounding amount of the solvent compounded in the composition of the present invention can be minimized. This is a great feature of the present invention. The above effect cannot be obtained with only one of (x) and (y).

The above two components (x) and (y) may be one type of each component or a combination of two or more types. Then, as (x) + (y) which is the sum of the two components, 11 to 35% of the total composition
It is mixed in the ratio of. If it is less than 11%, the above effect cannot be sufficiently obtained, while if it exceeds 35%, it becomes highly viscous and causes problems during filling work, and low temperature stability deteriorates, and separation and layer separation are easy. Because it will be. Then, it is particularly preferable to combine both in a weight ratio of (x) :( y) = 9: 16 to 1:24 from the viewpoint of low temperature stability during storage. The above two components (x),
Both (y) are nonionic surfactants that have not been conventionally used in neutral detergents because they have poor detergency, but in the present invention, the two are balanced within a specific range. By considering and combining specific amounts,
The above-mentioned excellent effect is brought out without impairing the cleaning property.

As the anionic surfactant which is the component (B) of the present invention, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkane sulfonate, α
-Olefin sulfonate is used . Examples of the alkyl sulfate ester salts include sodium lauryl sulfate ester, triethanolamine lauryl sulfate ester, ammonium lauryl sulfate ester, potassium lauryl sulfate ester, lithium lauryl sulfate ester, barium lauryl sulfate ester, and the like. Is preferred. Examples of the alkyl ether sulfate ester salt include polyoxyethylene alkyl ether sulfate ester sodium, polyoxyethylene alkyl ether sulfate ester triethanolamine, polyoxyethylene alkyl ether sulfate ester ammonium, and the like. Sodium ether sulfate is preferred. The carbon number of the alkyl group is 10
16, especially 12 to 14 are preferable. Also,
The number of moles of ethylene oxide added to polyoxyethylene is preferably 2 to 5, and most preferably 2 to 3. They are,
They may be used alone or in combination of two or more. In particular, alkyl sulfate ester salt and alkyl ether sulfate ester salt are preferable, and when both are used in combination, the cleaning performance and the mild feeling to the hand are further improved. And the above-mentioned (B) component is 4 to the whole composition.
It is blended at a ratio of 10%. That is, if it is less than 4%, the detergency is poor, and if it exceeds 10%, the low temperature stability is deteriorated, and at the same time, the mild feeling to the skin cannot be maintained. The above alkyl sulfate ester salt (p)
And the alkyl ether sulfate ester salt (r) are combined, the weight ratio (p) :( r) of both is 4: 1 to.
It is preferable to set it to 1: 4. That is, when the amount of alkyl sulfate ester (p) exceeds the above range,
A tenderness on the skin tends to occur after using the cleansing composition, and when the amount of the alkyl ether sulfate (r) exceeds the above range, a sticky feeling on the skin tends to occur after using the cleansing composition. Because it will be done. In addition, those which do not contain the anionic surfactant are likely to easily separate and separate into layers, or to cause turbidity at low temperature.

Further, as the fatty acid alkanolamide which is the component (C) of the present invention, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, oleic acid diethanolamide, palm kernel Examples thereof include oil fatty acid diethanolamide. These may be used alone or in combination of two or more. Among them, it is preferable to use coconut oil fatty acid diethanolamide from the viewpoint of storage stability, that is, the transparency is maintained during storage and a layer is not formed.

The above fatty acid alkanolamide is blended in a proportion of 5 to 33%, preferably 10 to 26%, more preferably 10 to 20%, based on the whole composition.
Be compounded. If it is out of the above range, the composition is likely to be solidified at room temperature, or the composition may be easily separated, separated into layers, or turbid.

The higher alcohol-based concentrated neutral detergent composition of the present invention contains the above-mentioned components (A) to (C) as essential surfactant components, and together with these, other known surface-active agents. Agent components can be appropriately mixed. However, the concentration of the whole surfactant component including the above components (A) to (C) with respect to the composition must be set to 30 to 55%. That is, when the surfactant concentration is less than 30%, it cannot be said that there is a significant difference in concentration as compared with the conventional product, and the container cannot be made compact. Conversely, if the surfactant concentration exceeds 55%,
This is because the stock solution of the composition becomes turbid and the appearance is deteriorated, and the viscosity characteristics that are easy to use are not obtained.

Further, in the present invention, a pH adjusting agent is used as the component (D) together with the above-mentioned surfactant component.
Examples of the pH adjusting agent include citric acid, boric acid, sulfuric acid, hydrochloric acid, acetic acid, lactic acid, malic acid, etc. These may be used alone or in combination of two or more kinds. Of these, citric acid, boric acid, and sulfuric acid are particularly preferable from the viewpoints of low-temperature stability and pH stability over time.

The pH adjuster is to provide the acid necessary to keep the composition neutral. That is, p
A stock solution containing no H adjuster usually has a pH of 8 to 10.
However, since it has a bad effect on human skin as it is, it has been conventionally used.

Further, in the present invention, a solvent component is used as the component (E). Examples of the solvent component include lower alcohols such as ethanol, propylene glycol (PG), polyethylene glycol (PEG) and glycerin. Among them, ethanol and PG are preferable, and PG is particularly preferable.
Is the best.

The above solvent component is contained in an amount of 3 to 7 relative to the total composition.
It is blended in the ratio of % . That is, when the solvent component exceeds 7%, there are cases where solvent odor may condense composition, have name preferred as a product. Further , when the amount is 5% or less, the solvent odor is completely eliminated, but when the amount is less than 3%, the surfactant concentration is 5 which is the upper limit.
If you 5%, that of difficult to handle the viscosity is too high.

The thus-obtained higher alcohol-based concentrated neutral detergent composition of the present invention has a composition viscosity at 20 ° C. of 400 to 1100 cps, which has a low viscosity even though the surfactant component concentration is relatively high. Therefore, the efficiency of filling the pouch or the like is not impaired. Moreover, handling such as dilution is easy, and uniform dilution is possible. Moreover, the compounding amount of the solvent component is kept low, and there is no solvent odor. In addition, the composition has neither gelation nor solidification at low temperature, and has an excellent appearance and storage stability for a long period of time.

[0030]

As described above, the higher alcohol-based concentrated neutral detergent composition of the present invention can be used for cleaning dishes, cooking utensils, etc.
In a detergent used for washing vegetables and fruits, the surfactant component concentration is 30 to 55%, which is a relatively high concentration, but as the component (A), two special polyoxyethylene alkyl ethers are used. Type nonionic surfactant is used , and a specific anion is used as the component (B).
Since a surfactant is used , a gelation phenomenon and a low temperature solidification phenomenon do not occur, and a very stable quality can be maintained for a long period of time. Further, since the compounding amount of the solvent component can be suppressed to be low, a product having no solvent odor can be obtained. Further, since the stock solution has an appropriately low viscosity, it is possible to efficiently fill a container such as a pouch with the viscosity, and the viscosity at the time of use does not become too low. Moreover, since no expensive component material is used, there is an advantage that the cost can be kept low.

Among the above-mentioned components (A), particularly those in which higher alcohols 2 to 6 EO and higher alcohols higher alcohols 7 to 12 EO are combined in a weight ratio of 9:16 to 1:24 are the above. The effect is even better.

Among the anionic surfactants as the component (B), those using at least one of the alkyl sulfate ester salt and the alkyl ether sulfate ester salt are excellent in cleaning performance and mild feeling to the hand. Among them, a combination of the alkyl sulfate ester salt and the alkyl ether sulfate ester salt in a weight ratio of 1: 4 to 4: 1 produces particularly excellent effects.

Further, among the pH adjusters of the above-mentioned component (D), especially those using at least one acid selected from the group consisting of citric acid, boric acid and sulfuric acid, are stable at low temperature and with time of pH. It has excellent stability.

Next, examples will be described together with comparative examples. In Tables 1 to 17 below, which show the compositions of Examples and Comparative Examples, as a raw material, the pure content was 100.
When less than 10% is used, the numerical value showing the raw material composition is shown as a pure content.

[0035]

Examples 1 to 13 and Comparative Examples 1 to 14 Tables 1 to 6 below
A higher alcohol-based concentrated neutral detergent composition having the composition (weight basis, the same applies hereinafter) was prepared. Then, the obtained composition was evaluated for the following items, and the results are also shown in Tables 1 to 6 below.

[Appearance] The detergent composition was dried at room temperature (25
C.) and low temperature (5.degree. C.) for 7 days, the appearance was visually observed and evaluated. The evaluation criteria are as follows. ◎ ... Transparent, with no turbidity, separation, or separation. ○: A slight turbidity is generated as a whole, but there is a transparency, and no layer separation or separation is observed. B: No cloudiness and transparency, but no separation or separation is observed. X: Cloudy and no transparency, and separation and separation are observed.

[Fluidity] 200 ml of the detergent composition was put in a glass standard bottle having a capacity of 250 ml, and kept in a low temperature constant temperature bath (IN-81, manufactured by Yamato Scientific Co., Ltd.) set at 5 ° C. for 5 hours. It was taken out, tilted or turned upside down, and the fluidity was visually observed and evaluated. The evaluation criteria are as follows. ◎ ... It has fluidity and does not cause any problems in use. ◯: The fluidity is slightly inferior, but there is no problem in use. Δ: High viscosity and poor fluidity, making it difficult to handle in use. ×: Loss of fluidity, solidification and handling impossible.

[Viscosity] The viscosity at 20 ° C. was measured using a B type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

[Detergency] Tested according to JIS K3362 (improved re-nut method). In addition, based on the detergency (detergent concentration 1.5%) of the index detergent for JIS detergency determination,
The washing power was measured under the conditions of a measurement temperature of 30 ± 1 ° C. and an active ingredient detergent concentration of 0.04%, and the washing power was compared and evaluated. The evaluation criteria are as follows. A: Remarkably excellent. ○… Slightly excellent. Δ: Equivalent ×… Slightly inferior. XX ... Inferior.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

From the above results, it can be seen that all of the products of Examples 1 to 13 have excellent transparency and fluidity, and there is no problem in detergency. On the other hand, Comparative Examples 1-4, 6, 8-14
It can be seen that the product has problems in transparency and fluidity, and there is a problem in handling. The products of Comparative Examples 5 and 7 had no problem in terms of transparency and fluidity, but the detergent composition had a solvent odor because of a large blending ratio of the solvent components, which was not preferable as a product. .

[0047]

Examples 14 to 19 Further, as shown in Tables 7 and 8 below, the compounding ratios of the two kinds of polyoxyethylene alkyl ethers (x) and (y) as the component (A) were changed. A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Then, the obtained compositions were evaluated in the same manner as above, and the results are shown in Tables 7 and 8 below.

[0048]

[Table 7]

[0049]

[Table 8]

From the above results, two kinds of polyoxyethylene alkyl ethers (x) and (y) which are the component (A) are used.
It can be seen that it is preferable to set the mixing ratio of (x) :( y) to 1:24 to 9:16.

[0051]

Examples 20 to 29 Next, as shown in Tables 9 and 10 below, the kind of the polyoxyethylene alkyl ether (x) in the component (A) was changed. A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Therefore, the composition below the component (B) is omitted. Then, the obtained compositions were evaluated in the same manner as above, and the results are shown in Tables 9 and 10 below.

[0052]

[Table 9]

[0053]

[Table 10]

From the above results, it can be seen that as the polyoxyethylene alkyl ether (x), it is possible to use one having the addition mole number of ethylene oxide of 2 to 6.

[0055]

Examples 30 to 37 Next, as shown in Tables 11 and 12 below, the kind of the polyoxyethylene alkyl ether (y) in the component (A) was changed. A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Therefore, the composition below the component (B) is omitted. Then, the obtained compositions were evaluated in the same manner as above, and the results are shown in Tables 11 and 12 below.

[0056]

[Table 11]

[0057]

[Table 12]

From the above results, as the polyoxyethylene alkyl ether (y), the alkyl group has 10 carbon atoms.
In the range of up to 18, the number of moles of ethylene oxide added is 7
It can be seen that those up to 12 can be used.

[0059]

Examples 38 to 44 and Comparative Examples 15 and 16 Next, as shown in Tables 13 and 14 below, the type of the component (B) was changed. A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Then, while evaluating the obtained composition in the same manner as described above,
The mild feeling to the hand was also evaluated according to the method shown below. The results are also shown in Tables 13 and 14 below.

[Mild feeling for hand] 1g per sheet
25.5c diameter contaminated with refined beef tallow (manufactured by NOF CORPORATION)
Fifty m flat pottery plates were prepared. Then, to each of the 5 panelists, 1 person was used with 30 ° C lukewarm water in which the detergent composition was dissolved so that the concentration of the detergent active ingredient was 0.04%.
The flat plates were washed one by one, and the feel of the hand after washing was evaluated according to the following criteria. ◎… It is very refreshing without a feeling of refreshing. ○… Normal. △… Slightly tighter than usual. ×: There is a tight feeling and it is bulky.

[0061]

[Table 13]

[0062]

[Table 14]

From the above results, as the component (B), a combination of the alkyl sulfate ester salt (p) and the alkyl ether sulfate ester salt (r) at a weight ratio of 4: 1 to 1: 4 was used. It can be seen that it is suitable because it has an excellent mild feeling to. On the other hand, Comparative Examples 15 and 16 containing no component (B) had poor transparency and fluidity,
Not practical.

[0064]

Examples 45 to 47, Comparative Examples 17 and 18 Next, as shown in Table 15 below, the type of the component (C) was changed. A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Then, the obtained composition was evaluated in the same manner as above, and the results are also shown in Table 15 below.

[0065]

[Table 15]

From the above results, it is understood that various fatty acid alkanolamides can be used as the component (C).

[0067]

Examples 48 to 53, Comparative Example 19 Further, Table 1 below.
6, as shown in Table 17, the type of component (D) was changed.
A higher alcohol-based concentrated neutral detergent composition was prepared in the same manner as in Example 3 except above. Then, the obtained compositions were evaluated in the same manner as above, and the results are shown in Tables 16 and 17 below.

[0068]

[Table 16]

[0069]

[Table 17]

From the above results, it is understood that various acids can be used as the component (D). In particular, it is found that citric acid (see Example 3), sulfuric acid, and boric acid are preferably used because the transparency at a low temperature is maintained well.

Continuation of the front page (56) Reference JP-A-8-3587 (JP, A) JP-A-6-240292 (JP, A) JP-A-7-118695 (JP, A) JP-A-7-316589 (JP , A) JP-A-7-173491 (JP, A) JP-A-8-319500 (JP, A) JP-A-7-258691 (JP, A) Special Table 8-505413 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/00-17/08 A61K 7/075 A61K 7/50

Claims (5)

(57) [Claims] 1. A surfactant component comprising the following components (A) to (C) as essential components at a concentration of 30 to 55% by weight based on the total composition, and the following (D): ，
A higher alcohol-based concentrated neutral detergent composition containing the component (E) and having a composition viscosity at 20 ° C. of 400 to 1100 cps. (A) Polyoxy compound formed by combining 1 to 9% by weight of an ethylene oxide 2 to 6 mol adduct (x) with a higher alcohol and 7 to 12% by weight of an ethylene oxide 7 to 12 mol adduct (y) with a higher alcohol. Ethylene alkyl ether type nonionic surfactant 11 to 35% by weight. (B) Alkyl sulfate ester salt, alkyl ether sulfate
Ester salts, alkane sulfonates and α-olefins
At least one selected from the group consisting of
4-10% by weight of anionic surfactant. (C) 5-33% by weight of fatty acid alkanolamide. (D) pH adjuster. (E) Solvent component 3 to 7 % by weight . 2. The polyoxyethylene alkyl ether as the component (A), wherein (x) and (y) are (x):
The higher alcohol-based concentrated neutral detergent composition according to claim 1, which is combined in a weight ratio of (y) = 9: 16 to 1:24. 3. The higher alcohol-based concentrate according to claim 1, wherein the anionic surfactant as the component (B) comprises at least one of an alkyl sulfate ester salt (p) and an alkyl ether sulfate ester salt (r). Detergent composition. 4. The component (B) anionic surfactant comprises an alkyl sulfate ester salt (p) and an alkyl ether sulfate ester salt (r), wherein (p) and (r).
Are combined in a weight ratio of (p) :( r) = 1: 4 to 4: 1. The higher alcohol-based concentrated neutral detergent composition according to claim 3. 5. The higher alcohol system according to any one of claims 1 to 4, wherein the pH adjuster of the component (D) is at least one acid selected from the group consisting of citric acid, boric acid and sulfuric acid. Concentrated neutral detergent composition.