JP2003193098A - Liquid detergent composition for automatic flushing machine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid detergent composition for automatic flushing machines that includes no surfactant, is mildly alkaline despite that the detergent composition simply comprises a combination of two specific components, has excellent detergency, soil redeposition inhibitory performance, low foaming properties and shows excellent storage stability over a wide range of thermal environment. <P>SOLUTION: The liquid detergent composition mainly comprises (A) 5-18 mass % of amino acid salts, (B) 10-30 mass % of silicate salts and water but does not include any alkaline agent other then the silicate salts and any surfactant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition suitable for cleaning hard surfaces such as tableware, glass, ceramics, metals and plastics, and in particular, it has excellent cleaning performance even without containing a surfactant. And a liquid detergent composition having storage stability. More specifically, it relates to a liquid detergent composition suitable for use in an automatic washing machine such as an automatic dishwashing machine.

[0002]

[Prior Art] Traditionally, hotels, restaurants, schools,
2. Description of the Related Art Automatic dishwashers are widely used in hospitals, restaurants, catering companies, company cafeterias, etc. in order to efficiently wash used dishes. Further, not only tableware but also various manufacturing factories, processing factories, and the like, automatic washing machines are used to wash utensils, containers, plastic containers used for distribution, and the like.

Liquid detergents used in these automatic washing machines usually contain alkali metal hydroxides such as sodium hydroxide and potassium hydroxide in an amount of 10 to 50% by mass for the purpose of removing strong oil and fat stains. (Hereinafter abbreviated as “%”).

[0004]

However, the detergent containing the alkali metal hydroxide in an amount of more than 5% is a "non-medicinal deleterious substance" and requires careful handling from the viewpoint of safety. Further, the alkali metal hydroxide may erode the surface of glass tableware, blacken aluminum tableware and cooking utensils, tend to have insufficient cleaning effect on protein stains, etc. I have a problem.

Therefore, recently, in place of the above-mentioned alkali metal hydroxide, use of a milder alkali agent and blending of various surfactants having a high cleaning performance against oil and fat stains are required. However, many of the above surfactants are not suitable for nozzle-jet type mechanical cleaning through a pump because of a large amount of foaming, and many of them are easily decomposed by the alkali of the cleaning composition. Further, in such a surfactant that does not foam or decompose, the detergent composition itself causes separation / precipitation, which makes it difficult to obtain a homogeneous liquid detergent composition at the time of use. Furthermore, when the pH of the solution at the time of using the detergent composition used for this is adjusted from neutral to weakly alkaline,
The cleaning performance required for machine cleaning cannot be obtained, and
There are problems such as decay of the cleaning composition itself and generation of mold, bacteria, etc. inside the automatic dishwasher. On the other hand, it has been proposed to add a bactericidal agent or a cationic surfactant, but by itself, a sufficient antifungal effect, bactericidal effect,
The fact is that the cleaning performance is not obtained.

For example, Japanese Unexamined Patent Publication No. 56-45997 discloses an alkaline cleaner for cleaning hard surfaces, which contains 17 to 25% sodium hydroxide and 4 to 18% sodium 2-hydroxyethyliminodiacetate as essential components. Has been done. Although this product has excellent low-temperature stability, it has relatively strong alkalinity, and when other surfactant components or neutral salts are contained, it is difficult to maintain a homogeneous liquid.

Further, in Japanese Patent Laid-Open No. 2-55800,
Disclosed is a detergent comprising a detergent as a main component and a surface-active agent as an auxiliary washing component separated from each other, and a device for supplying the detergent. This product is weakly alkaline and has superior safety compared to conventional products, but since the detergent is separated into two or more types,
There is a problem that each component is not consumed in equal proportion and remains unevenly, and if trouble occurs in the operation of the dedicated detergent supply device, the mixing ratio of each component is disturbed and uniform washing cannot be obtained. is there.

Further, JP-A-6-33100 discloses a detergent for an automatic dishwashing machine, which contains a low-foaming nonionic surfactant, a washing builder and a specific aliphatic carboxylic acid as essential components. There is. Although this one contains a relatively large amount of low-foaming nonionic surfactant,
It has the advantage that the whole is homogeneous and stable,
It has only low temperature stability up to -6 ° C, not stability in wide temperature environment.

As described above, [1] has a milder alkaline property, [2] has excellent cleaning performance, particularly excellent cleaning performance against protein stains, [3] has low foaming properties, and [4] rinses. Preparation of a well-balanced cleaning agent that combines all the conditions such as excellent post-finishing properties (performance in which spots do not remain), [5] stable storage in a wide range of temperature environments, etc. It is not easy to do, and if the component composition is changed to obtain a good balance, it is necessary to add another component, which tends to make the system more complicated and costly. It is strongly desired to develop a detergent composition having a new composition that solves these problems.

The present invention has been made in view of the above circumstances, and has a simple composition in which a surfactant is not contained at all and a specific two components are combined, but it is mildly alkaline and has a simple composition. An object of the present invention is to provide an excellent liquid cleaning composition for an automatic washing machine, which has excellent cleaning performance, anti-soil redeposition performance, low foaming performance, and storage stability in a wide temperature environment.

[0011]

In order to achieve the above object, the present invention provides (A) aminocarboxylic acid salt 5 to 18% by mass, (B) silicate 10 to 30% by mass and (C) water. First, a liquid cleaning composition for an automatic cleaning machine, which comprises, as a main component, no alkaline agent other than the above-mentioned silicate and a surfactant.
The summary of

In the present invention, in particular, the mixing ratio (A: B) of the above-mentioned A component and B component is 1: 1.2.
The second gist is a liquid detergent composition for an automatic washing machine, which is set to 1: 3.5, wherein the aminocarboxylic acid salt of the component A is trisodium nitrilotriacetate, and the silicic acid of the component B is used. A third aspect is a liquid detergent composition for an automatic washing machine, wherein the salt is at least one of potassium silicate and sodium silicate.

Further, the present invention is particularly advantageous among them.
In addition, the silicate of the B component is xM ₂O ・ ySiO
₂(M: at least one of potassium and sodium)
, And x: y = 2: 1 to 1: 3.5
A fourth aspect of the present invention is a liquid detergent composition for a washing machine.

[0014]

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

The liquid detergent composition for an automatic washing machine of the present invention has, as its main component, an aminocarboxylic acid salt (component A).
And silicate (B component) and water (C component) are used, and an alkali agent other than the silicate and a surfactant are not used,
This is a great feature.

First, as the aminocarboxylic acid salt as the component A, nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid (EDTA), propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycoletherdiaminetetraacetic acid. Acetic acid, triethylenetetramine hexaacetic acid, bis (2-hydroxyphenylacetic acid) ethylenediamine, iminodiacetic acid,
Examples thereof include a mixture of aspartic acid diacetic acid and peptogluconic acid oligosaccharide, an alkali metal salt such as glutamic acid diacetic acid and ethylenediaminedisuccinic acid, an alkaline earth metal salt, an ammonium salt, or an alkanolamine salt. Among these, trisodium nitrilotriacetate, tetrasodium ethylenediaminetetraacetate, and tetrasodium aspartate diacetate are particularly preferably used.

The compounding amount of the above-mentioned aminocarboxylic acid salt is set within the range of 5 to 18% with respect to the whole. That is,
If the blending amount is less than 5%, the cleaning performance and the ion sequestration performance cannot be obtained, and if it exceeds 18%, the overall balance becomes poor and the synergistic effect with the silicate as the B component is further increased. Because you cannot get it.

The silicate as the component B is represented by the general formula M ₂ O.nSiO ₂ , and examples thereof include sodium silicate and potassium silicate. In the present invention, it is particularly preferable to use sodium silicate, and SiO ₂ / M
_The molar ratio of ₂ O is preferably set to 0.5 to 3.5. That is, if the above molar ratio is less than 0.5, the alkalinity of the silicate becomes too strong, which is not preferable for the environment. Above all, in order to give a good finish to the surfaces of glass tableware and aluminum tableware / cookware, the above molar ratio is preferably 1.1 mol or more.

The silicate having a suitable molar ratio may be selected from commercially available products. For example, in the case of sodium silicate, an appropriate amount can be obtained by adding sodium hydroxide to JIS No. 3 sodium silicate. The molar ratio can be adjusted. Furthermore, by adding sodium hydroxide and potassium hydroxide, an arbitrary mixture of sodium silicate or potassium silicate can be obtained.

The compounding amount of the above silicate is 1 with respect to the whole.
It is set within the range of 0 to 30%. That is, if the blending amount is less than 10%, the cleaning performance becomes insufficient, and conversely 30%.
If it exceeds, the balance as a whole is deteriorated and the synergistic effect with the aminocarboxylic acid salt as the component A cannot be obtained any more. And, in particular, the mixing ratio (A: B) of the aminocarboxylic acid salt and the silicate is
When the ratio is set to 1: 1.2 to 1: 3.5, the liquid detergent has a good overall balance, is very stable, and has excellent detergency.

The water used together with the components A and B includes tap water, soft water, ion-exchanged water, pure water, purified water and the like, preferably soft water, ion-exchanged water and pure water. To be The above "water" refers to the sum of water contained in the form of crystallization water or an aqueous solution derived from each component constituting the detergent composition and water added from the outside,
It is blended in the detergent composition so as to be 100% as a whole.

In the liquid detergent composition of the present invention, fragrance, dye, metal corrosion inhibitor, water-soluble solvent and the like can be used as optional components.

The liquid detergent composition of the present invention obtained by using these essential components and optional components uses only two components, an aminocarboxylic acid salt and a silicate, as a cleaning component, and limits the blending ratio of these components. Since it has been used for a long time, it achieves excellent cleaning performance, especially cleaning performance against protein stains, low foaming property, and storage stability in a wide temperature environment, and also has excellent finish after rinsing. ing. And since silicate is used as the alkali agent instead of alkali metal hydroxide, it is not only highly safe, but also does not adversely affect the surface of glass tableware and aluminum tableware / cookware. .

Therefore, the liquid cleaning composition of the present invention is suitable for cleaning hard surfaces such as glass, ceramics, metals and plastics. Further, it is not limited to tableware, and can be used as an automatic washing machine for washing instruments and containers in various manufacturing factories, processing factories, etc., and plastic containers used for distribution. In addition, it can be preferably used for washing hard surfaces such as tiles and floors of food factories and food processing factories, washing containers such as glass bottles and beer bottles for beverages, and washing metal surfaces. In particular, it is suitable for use in automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like.

Next, examples will be described together with comparative examples.

[0026]

Examples 1 to 21, Comparative Examples 1 to 13 Tables 1 to 1 below
The detergent composition having the composition shown in 0 was prepared, the pH was measured, and 7 items of storage stability, low foaming property, detergency, finish after cleaning, effect on glass surface, and effect on aluminum surface were evaluated. did. The results are also shown in Tables 1 to 10 below. In addition, the test method of each item,
The evaluation method is as shown below.

[Measurement of pH] -Measurement method Using a pH meter (pH METER F-12, manufactured by Horiba, Ltd.), a stock solution of the detergent composition prepared according to JIS Z-8802 and ion-exchanged water were prepared. PH of diluted 0.2% diluted solution at 25 ° C
The value was measured.

[Storage Stability] Test Method The prepared detergent composition was put in a 100 ml polyethylene bottle and placed in an atmosphere of 50 ° C. in a thermostat (SLI-4S, manufactured by Sunaka Rika Kogyo Co., Ltd.). -15 ° C with an incubator (MDF-U332, manufactured by Sanyo Electric Co., Ltd.)
Under an atmosphere of, and stored in that state for 1 month. Then, the appearance was visually observed and evaluated according to the following evaluation criteria. -Evaluation criteria ⊚: After 1 month, there was no change in appearance such as separation or precipitation. ○: After 1 month, a slight change in appearance such as separation and precipitation was observed. Δ: After 2 weeks, a slight change in appearance such as separation and precipitation was observed. X: After 1 week, there was a change in appearance such as separation or precipitation.

[Low foaming property] Test method The prepared cleaning composition was used for an automatic dishwasher (D
W-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. Then, the foaming of the cleaning liquid was visually evaluated according to the evaluation criteria described below. * Operating conditions Detergent concentration: 0.15% Washing temperature: 60 ° C Washing course: Standard washing cycle (washing: 43 seconds, rinsing: 15 seconds) Hardness of tap water: (as CaCO ₃ ) 70-80 ppm ・ Evaluation criteria ◎ ... The bubbles are less than 50 mm from the liquid surface during operation, and the bubbles disappear promptly after the operation ends. ○: Bubbles are less than 50 mm from the liquid surface during operation, and disappear within 1 minute after the end of operation. B: The bubbles are 50 mm or more from the liquid surface during the operation, but the bubbles disappear within 1 minute after the completion of the operation. × ... Regardless of the height of bubbles during operation, the bubbles remained without disappearing after 1 minute from the end of operation.

[Detergency] ・ Test method The prepared detergent composition is used for an industrial dishwasher (D
W-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. Then, a set of 10 ceramic dishes, which are the following objects to be cleaned, was cleaned, and the cleaning performance was evaluated according to the evaluation criteria described below. Two types of stains, standard stains and egg yolk stains, were prepared, and each stain was evaluated for cleaning. * Operating conditions Detergent concentration: 0.20% Washing temperature: 60 ° C Rinse temperature: 80 ° C Washing course: Standard washing cycle (washing: 43 seconds, rinsing: 15 seconds) Hardness of tap water: (as CaCO ₃ ) 70-80 ppm Standard dirt: After 70 parts by mass of margarine (hereinafter abbreviated as "part") is dissolved by heating, 15 parts of powdered milk, 5 parts of non-fat milk and 10 parts of wheat flour are added to make uniform, and further 30 parts of water is added to form a paste. And made it standard stain. Egg yolk stain: Egg yolk was taken out from all eggs and thoroughly mixed to obtain egg yolk stain. Object to be washed: The above standard stain was adhered to a ceramic dish having a diameter of 20 cm so that the standard stain became 8 g / sheet, and dried at room temperature for 1 hour.・ Evaluation criteria ◎ ... 90% or more stain removal ○ ... 70 to less than 90% stain removal Δ ... 50 to less than 70% stain removal × ... less than 50% stain removal

[Finishing property after washing] -Test method The prepared detergent composition is used for an industrial dishwasher (D
W-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following conditions. Then, 10 glass cups, which are the objects to be cleaned shown below, were cleaned as a set, and the finished performance after cleaning was evaluated by the evaluation criteria described below. * Operating conditions Detergent concentration: 0.15% Washing temperature: 60 ° C Rinse temperature: 80 ° C Washing course: Standard washing cycle (washing: 43 seconds, rinsing 15 seconds) Hardness of water used: (as CaCO ₃ ) 70-80 ppm Washed product: Milk was poured into an 8 ounce glass cup (manufactured by Sasaki Glass Co., Ltd.) and left for 5 minutes. The milk was then discarded and air dried for 30 minutes without rinsing with water.・ Evaluation criteria: No water spots are observed. O: 1-2 water spots are seen. Δ: 3 to 5 water spots are seen. ×: Six or more water spots are seen.

[Effect on Glass Surface] Test Method A commercially available ordinary tumbler glass (made of soda glass) was immersed in the prepared detergent composition under the following conditions. Then, the state of the tumbler glass after immersion was visually observed and evaluated according to the following evaluation criteria. * Immersion conditions Detergent concentration: 0.20% Immersion temperature: 60 ° C Immersion time: 2 weeks ・ Evaluation criteria ⊙: No discoloration or corrosion is observed on the tumbler glass surface. ○: The surface of the tumbler glass is slightly discolored. Δ: The discoloration of the tumbler glass surface is large. X: Corrosion on the surface of the tumbler glass is large.

[Effect on Aluminum Surface] Test Method An aluminum test piece (product number A1050P, 100 mm × 20 mm) was immersed in the prepared detergent composition under the following conditions. Then, the state of the aluminum test piece after immersion was visually observed and evaluated according to the following evaluation criteria. * Immersion condition Detergent concentration: 0.20% Immersion temperature: 60 ° C Immersion time: 3 hours-Evaluation criteria ⊚ ... No discoloration or corrosion is observed on the aluminum surface. ○: The aluminum surface is slightly discolored. Δ: The discoloration of the aluminum surface is large. X: The aluminum surface is significantly corroded.

In Tables 1 to 10 described later, the details of the components used and their effective net contents (%) are as follows, and the numerical values in the table are converted into 100% of the effective net contents. It is shown. Incidentally, "water" in the table is the sum of water contained in the form of crystallization water or an aqueous solution derived from each component constituting the detergent composition and water added from the outside, and the entire detergent composition. It is shown as a balance to be 100%.

[Component A] -Tritrilotriacetate trisodium salt Trade name: Trilon A92R, manufactured by BASF. -Ethylenediaminetetraacetic acid tetrasodium trade name: Trilon B, manufactured by BASF. -Aspartic acid tetrasodium diacetate Brand name: Asda 4Na (45% aqueous solution), manufactured by Mitsubishi Rayon Co., Ltd. -Sodium iminodiacetate product name: CHIREST E-20 (20% aqueous solution), manufactured by CREST. -Sodium tripolyphosphate Trade name: Wandet B, manufactured by Nippon Kagaku Co., Ltd. [B component] -Sodium silicate trade name: J sodium silicate No. 3 (35.5% aqueous solution), manufactured by Fuji Chemical Co., Ltd. Na ₂ O · 3.2 SiO ₂ · potassium silicate 1 Trade name: 1K potassium silicate (50.25% aqueous solution), manufactured by Nippon Kagaku Kogyo Co., Ltd. K ₂ O · 2SiO ₂ · potassium silicate 2 Product name: OK55 (55% aqueous solution), manufactured by Nippon Kagaku Kogyo Co., Ltd. 2K ₂ O · SiO ₂ · potassium silicate 3 Trade name: 2K potassium silicate (29.5% aqueous solution), manufactured by Nippon Kagaku Kogyo Co., Ltd. 3.5K ₂ O ・ SiO ₂・ Sodium carbonate Product name: Soda ash, manufactured by Central Glass Company.・ Sodium hydroxide product name: Pearl caustic soda, manufactured by Central Glass Co., Ltd.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

[Table 9]

[0045]

[Table 10]

From the above results, it is understood that all of the example products show excellent characteristics in all evaluation items.

[0047]

INDUSTRIAL APPLICABILITY As described above, the liquid detergent composition for an automatic washing machine of the present invention is excellent in that it does not contain an alkali agent other than silicate and does not contain any surfactant. Cleaning performance, especially excellent cleaning performance for proteins,
The liquid detergent composition has anti-soil redeposition performance and storage stability, and has a reduced impact on the environment.
Further, it is possible to provide a liquid detergent composition having excellent finish properties after washing and rinsing. And since silicate is used as the alkaline agent instead of alkali metal hydroxide, it is not only highly safe, but also does not adversely affect the surface of glass tableware and aluminum tableware / cookware. .

Therefore, the detergent composition for an automatic washing machine of the present invention is used for washing hard surfaces such as tableware, glass, ceramics, metal and plastic, and is not limited to tableware, and is used in various manufacturing factories, processing factories and the like. It can also be used as an automatic washing machine for washing containers, containers, and plastic containers used for distribution. Besides, it can be widely used for washing hard surfaces such as tiles and floors of food factories and food processing factories, container washing of glass bottles / beer bottles for beverages, metal surface washing and the like. In particular, it is suitable for use in automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinji Maruyama             2-1-1 Yoyogi, Shibuya-ku, Tokyo             -Paul Co., Ltd. F term (reference) 3B201 AA46 BB92                 4H003 BA12 DA05 DA19 EA15 EB13                       EB15 EB16 ED02 FA01 FA02                       FA15 FA16 FA19 FA21 FA28

Claims (4)

[Claims] 1. An alkaline agent other than the above-mentioned silicate and a surface active agent containing (A) an aminocarboxylic acid salt of 5 to 18% by mass, (B) a silicate of 10 to 30% by mass and (C) water as main components. A liquid detergent composition for an automatic washing machine, which is characterized by containing no agent. 2. A blending ratio of the component A and the component B (A:
The liquid detergent composition for an automatic washing machine according to claim 1, wherein B) is set to 1: 1.2 to 1: 3.5. 3. The automatic according to claim 1, wherein the aminocarboxylic acid salt of component A is trisodium nitrilotriacetate, and the silicate of component B is at least one of potassium silicate and sodium silicate. Liquid cleaning composition for washing machine. 4. The component B silicate is xM ₂ O · y.
SiO _2: indicated by (M least one potassium and sodium), and x: y = 2: 1~1: 3.5 a liquid for automatic washing machine according to any one of claims 1 to 3, Cleaning composition.