JPH11269495A - Detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent compsn. which is suitable for cleaning hard surfaces of household goods, tanks and pipelines in factories, and metal and plastic articles soiled with oils, etc., and is excellent esp. in detergency and biodegradability. SOLUTION: This compsn. contains an alkali metal hydroxide, an alkali salt of glutamic acid-diacetic acid, and a gluconate. The sum of the amts. of the alkali salt of glutamic acid-diacetic acid and the gluconate is at least 3 pts.wt. based on 100 pts.wt. alkali metal hydroxide, and the wt. ratio of the former salt to the latter is (30/70)-(90/10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition suitable for cleaning hard surfaces of fixtures, tanks and pipes of various factories, metal products and plastic products contaminated with oils, etc. The present invention relates to a hard surface cleaning composition having excellent microbial degradability.

[0002]

2. Description of the Related Art Various bottles such as beer bottles and milk bottles,
Various types of food production equipment such as tanks and pipes in food factories, and metal and plastic products such as ovens and grills with heavy oil stains are complicated in shape and are installed in immovable places. When cleaning dirt attached to the hard surface, it must be cleaned by means such as immersion in the cleaning solution, circulation of the cleaning solution, or spraying of the cleaning solution, and strong cleaning power for applying this cleaning. Agents are desired.

[0003] As this type of detergent, ethylenediaminetetraacetate (EDTA) or sodium gluconate is conventionally blended with an alkaline aqueous solution containing 1 to 5% by weight of sodium hydroxide. A cleaning agent containing a surfactant or the like for the purpose of suppressing foaming is used.

However, the detergent containing EDTA is E
Detergent power is enhanced by the strong chelate-producing ability of DTA, but EDTA is hard to be decomposed by microorganisms. Therefore, disposal of used waste liquid as it is poses a problem in terms of environmental conservation.

Further, in a detergent containing sodium gluconate, since sodium gluconate itself is easily decomposed by microorganisms, waste liquid after use can be treated with microorganisms, and thus, there is no problem in environmental conservation. Poor detergency, not suitable for cleaning hard surfaces (objects to be cleaned) with heavy dirt.

Further, a detergent composition comprising an alkali metal hydroxide and glutamic acid diacetate (GLDA) having microbial degradability is also known. This detergent composition also has no environmental problems, but has a lower detergency than a detergent containing EDTA, and therefore is not suitable for cleaning hard surfaces with heavy stains.

[0007] Further, a detergent composition comprising an alkali metal hydroxide, GLDA having biodegradability, and hydroxyacetate is also known. (JP-A-9-22
No. 1697)

[0008] The detergent composition is excellent in detergency, and
Although excellent in degradability by microorganisms, hydroxyacetate is expensive and difficult to put into practical use.

Further, there is known a detergent composition comprising an alkali metal hydroxide and an alkali metal salt of L-aspartic acid-N, N-diacetate and an alkali metal gluconate. (Japanese Patent Application Laid-Open No. 9-176694)

[0010] This detergent composition is excellent in microbial degradability,
In addition, the cleaning effect is high, but only the addition of the alkali metal L-aspartate-N, N-diacetate and the alkali metal gluconate produces a cleaning effect, but no synergistic cleaning effect. .

[0011]

In view of these circumstances, there has been a strong demand in recent years to develop a detergent composition which is easily decomposed by microorganisms and has excellent detergency.

Accordingly, an object of the present invention is to provide a hard surface cleaning composition which is excellent in the decomposability by microorganisms and has a large detergency, and which has the above-mentioned disadvantages of the prior art and which is improved. It is in.

[0013]

According to the present invention, in a detergent composition containing an alkali metal hydroxide, in addition to the alkali metal hydroxide, glutamic acid diacetate and a glutamic acid diacetate are further provided. It is characterized in that gluconate is additionally contained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

As described above, the feature of the present invention is that the alkali metal hydroxide contains both glutamic acid diacetate and gluconate, and the synergistic effect of the combination of these two components enhances the cleaning effect. In addition to increasing the biodegradability of the two components, the microbial degrading effect can be enhanced, thereby improving the environmental preservation.

The alkali metal hydroxide used in the present invention is a hydroxide of various alkali metals, such as sodium hydroxide and potassium hydroxide.

Glutamic acid diacetate (GLDA) used in the present invention is a salt of an amino acid derivative (glutamic acid derivative) represented by the following general formula.

[0018]

Embedded image (Salts, potassium, ammonium salts,
Examples thereof include amine salts such as monoethanolamine and morpholine, and each salt may be the same or different. )

Preferred examples of the above glutamic acid diacetate (GLDA) in the present invention include L-glutamic acid diacetate (L-GLDA), particularly sodium L-GLDA.

This GLDA is synthesized by a method of subjecting glutamic acid, preferably L-glutamic acid, obtained by fermentation of starch, saccharides or the like, to dechlorination condensation with, for example, a known Strecker reaction or monochloroacetic acid.

Further, the gluconate used in the present invention is an alkali salt of hydroxycarboxylic acid represented by the following general formula.

[0022]

Embedded image (Salts, potassium, ammonium salts,
Examples thereof include amine salts such as monoethanolamine and morpholine. )

A preferred example of the gluconate in the present invention is sodium gluconate.

The content of the above glutamic acid diacetate and gluconate is not less than 3 parts by weight, preferably not more than 3 parts by weight, based on 100 parts by weight of the alkali metal hydroxide.
-30 parts by weight, and in the case of such a total content, a strong cleaning effect by a two-component synergistic effect can be obtained.

The content ratio of the above-mentioned alkali glutamic acid diacetate and gluconate is 30:70 to 9 by weight.
0:10, preferably 30:70 to 80:20, more preferably 40:60 to 60:40,
By such a content ratio, a strong cleaning effect by a two-component synergy can be obtained.

The detergent composition of the present invention can further improve the cleaning effect by containing a nonionic surfactant, an alkali salt of a phosphonic acid and an alkali salt of a polycarboxylic acid alone or in combination of two or more. Can be.

Although any nonionic surfactant may be used, it is preferably a polyethylene glycol type nonionic surfactant, particularly a polyoxyethylene alkyl ether type. This content is preferably at least 1 part by weight based on 100 parts by weight of the alkali metal hydroxide.

The alkali phosphonic acid salt improves the dispersibility, and is, for example, a compound having a nitrogen atom in the molecule and / or a compound having a phosphonoalkylcarboxylic acid structure. It is a compound having a nitrogen atom in it. This content is 2 parts by weight or more based on 100 parts by weight of the alkali metal hydroxide as one or both of these contents.

The alkali salt of a polycarboxylic acid is not particularly limited, but an alkali metal salt of a copolymer of acrylic acid and maleic acid is preferable in consideration of solubility in an aqueous alkali solution and a washing effect, and particularly, a molecular weight of 2,000 to 5,000.
Are preferred. This content is preferably at least 2 parts by weight based on 100 parts by weight of the alkali metal hydroxide.

In the present invention, bleaching agents such as hypochlorite and dichloroisocyanurate, and defoamers such as surfactants can be added in optional amounts.

The detergent composition of the present invention comprising the above-described components is prepared in advance as a high-concentration aqueous solution, and is diluted to a desired concentration before use. In consideration of the degree of dirt on the object to be cleaned, the purpose of cleaning, the type and material of the object to be cleaned, the dilution concentration is usually appropriately set in the range of an aqueous alkali metal hydroxide concentration of about 1 to 5%. Selected.

For example, when cleaning a glass surface such as a glass bottle, it is necessary to achieve a desired cleaning effect while minimizing corrosion of the glass surface by a detergent. For this purpose, the concentration of the alkali metal hydroxide in the detergent is lowered and G
It is preferable to increase the total content of LDA and gluconate.

When cleaning the surface of a stainless steel tank or the inside of a pipe, it is preferable to increase both the concentration of the alkali metal hydroxide and the concentrations of GLDA and gluconate. At this time, the content ratio of GLDA and gluconate is preferably in the range of 40:60 to 60:40.

Further, when cleaning metal surfaces which are mainly contaminated with organic substances such as oils, the concentration of alkali metal hydroxide is reduced, and the total content of GLDA and gluconate is increased. It is preferable to use an auxiliary means such as the above or to soak for a long time for washing. In this case, GL
The content ratio of DA and gluconate is 80:20 to 60:
A range of 40 is suitable.

[0035]

Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 Samples 1 to 6 of the present invention and Comparative Examples 1 to 4 having the respective formulations shown in Table 1 were prepared.

On the other hand, a 10% aqueous suspension of diatomaceous earth is evenly applied to a glass plate and dried by heating at a temperature of 105 ° C. for 8 hours to produce an artificially stained plate. A cleaning performance test was performed on Samples 1 to 6 and Comparative Examples 1 to 4.

The test was performed as follows. First, 75
The above-mentioned artificial soil plate was immersed in each sample solution heated to 10 ° C. for 10 minutes, and after washing, the artificial soil plate was pulled out of each sample solution, rinsed with warm water, dried sufficiently, and this artificial soil was dried. The remaining amount of soil on the plate surface was measured using a gloss meter.

Next, the cleaning efficiency was calculated from the measured value and the measured value of the glossiness of the artificial soil plate before cleaning, and the cleaning performance was evaluated from the value (%) of the cleaning efficiency. The results are shown in Table 1. Further, the relationship between the content ratio of each sample and the cleaning efficiency (%) is shown in the graph of FIG.

In each of the components shown in Table 1, glutamic acid diacetate used was one synthesized by the above-mentioned method, and sodium hydroxide (NaOH) and sodium gluconate each used a primary reagent. G in Table 1
LDA, GNA and EDTA are: GLDA: sodium L-glutamate diacetate GNA: sodium gluconate EDTA: sodium ethylenediaminetetraacetate

The cleaning efficiency (%) indicates the average value of the test results performed on five artificially soiled plates. Each sample was diluted with water having a calcium carbonate concentration of 100 ppm hardness.

[0042]

[Table 1]

From Table 1 and FIG. 1, the samples of the present invention Nos. 1 to 6
It can be seen that the cleaning efficiency was significantly improved in each case. In particular, a composition comprising sodium hydroxide and GLDA (Comparative Example 1), a composition comprising sodium hydroxide and sodium gluconate (Comparative Example 2), and sodium hydroxide, GLDA and sodium gluconate Even with these three components, the cleaning efficiency of the sample of the present invention showed a remarkably large value as compared with the cleaning efficiency of the composition (Comparative Example 3) in which the content ratio of GLDA and sodium gluconate was 20:80. I have.

Further, from Table 1 and FIG. 1, it can be seen from the samples of the present invention, particularly, the samples having a content ratio of GLDA and sodium gluconate of 80:20 to 40:60 (samples of the present invention Nos. 2 to 2).
5) has strong detergency, sodium hydroxide and E
A high cleaning effect equivalent to that of the cleaning agent containing DTA (Comparative Example 4) was observed.

Example 2 Samples 7 to 9 of the present invention each containing a surfactant shown in Table 2 and Comparative Example 5 containing no surfactant were prepared.
Although the sample of Comparative Example 5 was a detergent composition according to the present invention, since it was a comparative test for the presence or absence of a surfactant, it was used as a comparative sample.

The test method was the same as in Example 1, except that the immersion time was set to 5 minutes and the conditions were strict to reduce the value of the cleaning efficiency. The same artificially soiled plate as in Example 1 was used as the object to be cleaned. Table 2 shows the results.

In Table 2, the same NaOH, GLDA and GNA as in Example 1 were used. The surfactants are secondary alcohol ethoxylates having an HLB of 12 or 16 (Adekator SO 120 and SO 16).
No. 0, manufactured by Asahi Denka Kogyo Co., Ltd.) and a non-ionic surfactant of primary alcohol ethoxylate HLB13 (ADEKATOL L09, manufactured by Asahi Denka Kogyo Co., Ltd.). Table 2 shows the content ratio of GLDA and GNA of each sample in Table 2.
, But are all 50:50.

[0048]

[Table 2]

From the results in Table 2, it was found that sodium hydroxide, GL
It can be seen that the washing efficiency was significantly improved by adding a polyethylene glycol type nonionic surfactant to the sample of the present invention comprising DA and sodium gluconate (mixing ratio: 50:50).

Example 3 Samples 10 to 14 of the present invention and Samples 6 to 8 of Comparative Examples each having the composition shown in Table 3 were prepared.

On the other hand, a stainless steel plate is immersed in a coffee solution containing milk fat, heated for a long time to adhere sewage to the surface of the stainless steel, and aged to produce an artificially soiled plate.
The cleaning performance test of the present invention samples 10 to 14 and comparative examples 6 to 8 was performed using this artificial soil plate.

The test was performed as follows. First, the artificial soil plate was washed with each sample aqueous solution having a hardness of 60 ppm at a temperature of 80 ° C. and a stirring speed of 250 rpm for 30 minutes, and then the washed artificial soil plate was rinsed with warm water and dried sufficiently. After that, the remaining amount of dirt on the surface of the artificially soiled plate was measured by glossiness.

Next, the cleaning efficiency was calculated from the measured value and the measured value of the glossiness of the artificial soil plate before cleaning, and the cleaning performance was evaluated from the value (%) of the cleaning efficiency. The results are shown in the table. Further, the relationship between the content ratio of each sample and the cleaning efficiency (%) is shown in the graph of FIG.

The components shown in Table 3 were the same as in Example 1. The cleaning efficiency in Table 3 is an average value of the test results performed on five artificially soiled plates.

[0055]

[Table 3]

From the results shown in Table 3 and FIG. 2, a sample composed of two components, sodium hydroxide and GLDA (Comparative Sample 6),
A sample consisting of two components, sodium hydroxide and sodium gluconate (Comparative Sample 8), and sodium hydroxide, G
Even with the three components of LDA and sodium gluconate, the content ratio of GLDA and sodium gluconate is 2
It can be seen that the cleaning efficiency of the sample according to the present invention (sample 10-14 of the present invention) is remarkably improved as compared with the sample consisting of 0:80 (sample 7 of the comparative example).

In the sample according to the present invention, GL
DA: sodium gluconate content ratio is 80:20
In the case of ５０50: 50 (samples 11 to 13 of the present invention), it was confirmed from Table 3 and FIG. 2 that they had strong detergency.

Example 4 Samples 15 to 22 of the present invention each containing a dispersant shown in Table 4 and Comparative Sample 9 containing no dispersant were prepared.
The sample of Comparative Example 9 was a detergent composition according to the present invention, but was a comparative test for the presence or absence of a dispersant.

The test method was the same as in Example 1, except that the immersion time was set to 5 minutes and the conditions were strict in order to reduce the value of the cleaning efficiency. The same artificially soiled plate as in Example 3 was used as the object to be cleaned. Table 4 shows the results.

In Table 4, the same NaOH, GLDA and GNA as in Example 1 were used. The dispersant is a neutralized sodium hydroxide of each of the following dispersants 1, 2 and 3. Dispersant 1: Phosphonate composed of 2-phosphonobutane-1,2,4-tricarboxylic acid, Bayhibit AM manufactured by Bayer AG. Dispersant 2: Aminotrimethylenephosphonic acid, manufactured by Monsanto Dequest 2000
. Dispersant 3: a polycarboxylate composed of a copolymer of acrylic acid and maleic acid, which is Sokaran CP manufactured by BASF
12S (Sokalam CP12S, molecular weight 3000). The content ratio between GLDA and GNA is 75:25.

[0061]

[Table 4]

From the results shown in Table 4, sodium hydroxide, GL
By adding a dispersant such as an alkali phosphonate or a polycarboxylic acid to the composition of the present invention comprising DA and sodium gluconate (content ratio of 75:25), the washing efficiency is remarkably improved. Is recognized.

REFERENCE EXAMPLES Reference samples 1 to 3 shown in Table 5 were prepared for reference. In Table 5, ASDA is L-aspartic acid-N, N-diacetate sodium salt disclosed in JP-A-9-176694 disclosed as a prior art, and in this reference example, these two components of ASDA and GNA with respect to NaOH were used. A test was performed to determine whether the combination provided a synergistic cleaning effect. The results are shown in Table 5.

[0064]

[Table 5]

From Table 5, it can be seen from Table 5 that the greater the input amount of ASDA, the higher the washing efficiency, and that an additive effect rather than a synergistic effect is observed. Was. For this reason, the use of ASDA and GNA requires a higher content than GLDA and GNA.

[0066]

As described above, the hard surface cleaning composition according to the present invention exhibits a synergistic cleaning effect by the combined use of gluconate and glutamic acid diacetate, and is comparable to a detergent containing EDTA. It is most suitable for cleaning various bottles, food production equipment such as tanks and pipes of food factories, and metal products and plastic products with severe oil stains.

Further, the composition for cleaning a hard surface according to the present invention has the following features:
The waste liquid is decomposed by microorganisms and there is no problem in terms of environmental protection by disposal.As a versatile cleaning agent that can replace the conventional cleaning agent containing EDTA, its utility value is extremely high. It greatly contributes to the technical field.

[Brief description of the drawings]

FIG. 1 is a graph showing the cleaning efficiency of diatomaceous earth soil on a glass surface at various content ratios of gluconate and GLDA.

FIG. 2 is a graph showing the cleaning efficiency of coffee stains on a stainless steel surface at various content ratios of gluconate and GLDA.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shin Saito 2-3-3 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Showa Denko KK Kawasaki Plant (72) Inventor Toru Yamamoto 2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture No.3 Showa Denko KK Kawasaki Plant

Claims (9)

[Claims] 1. A hard surface cleaning composition comprising an alkali metal hydroxide, glutamic acid diacetate and gluconate. 2. The hard surface cleaning composition according to claim 1, wherein the total content of glutamic acid diacetate and gluconate is at least 3 parts by weight based on 100 parts by weight of the alkali metal hydroxide. 3. The hard surface cleaning composition according to claim 1, wherein the content ratio of glutamic acid diacetate to gluconate is in the range of 30:70 to 90:10 by weight. 4. The hard surface cleaning composition according to claim 1, wherein the glutamic acid diacetate is L-glutamic acid diacetate. 5. The hard surface cleaning composition according to claim 1, wherein both glutamic acid diacetate and gluconate are sodium salts. 6. The cleaning composition according to claim 1, further comprising one or more selected from the group consisting of a nonionic surfactant, an alkali phosphonate, and an alkali polycarboxylate. Hard surface cleaning composition. 7. The method according to claim 6, wherein the nonionic surfactant is of a polyethylene glycol type, and its content is at least 1 part by weight based on 100 parts by weight of the alkali metal hydroxide. The hard surface cleaning composition according to any one of the preceding claims. 8. The method according to claim 6, wherein the alkali salt of phosphonic acid is a compound having a nitrogen atom in the molecule and / or a compound having a structure of phosphonoalkyl carboxylic acid, and the content of either or both of these compounds is reduced. The hard surface cleaning composition according to claim 6, wherein the amount is at least 2 parts by weight based on 100 parts by weight of the alkali metal hydroxide. 9. The method according to claim 6, wherein the alkali salt of the polycarboxylic acid is an alkali salt of a copolymer of acrylic acid and maleic acid, and the content of the alkali metal hydroxide is 100%.
The hard surface cleaning composition according to claim 6, wherein the amount is at least 2 parts by weight based on parts by weight.