JP5832189B2 - Rinsing accelerator for hard surface cleaner - Google Patents

Description

The present invention relates to an improvement in rinsing properties of a hard surface detergent excellent in foaming and detergency.

The explosive growth of the population since the end of the 19th century is unrelenting, and after 2050, the world's population is expected to exceed 10 billion. This explosive population increase is expected to lead to a shortage of various resources on the earth. In Japan, it is predicted that water resources that have been stably supplied will soon be insufficient. In such a situation, there is an increasing demand for a performance that can be rinsed with as little water as possible even in the detergent used for living a clean life in daily life.

In general, surfactants used in hard surface cleaners include anionic surfactants such as soap and alkyl sulfonic acid, nonionic surfactants such as polyoxyethylene alkyl ether, amine oxide type and betaine type amphoteric A wide variety of surfactants, such as surfactants, are used depending on their properties, or by devising the formulation. For example, since soap forms a metal soap scum, the removal ability of water stains is generally low. Therefore, an invention is disclosed in which soap is used in combination with a mixed system of a cationic surfactant and an amphoteric surfactant in order to enhance the metal scum removal capability to improve the cleaning performance and to improve the rinsing property ( Patent Document 1). However, although the use of soap can efficiently adsorb to the interface of the soil and reduce the interfacial tension with the soil by forming a complex with the cationic surfactant, it has been sufficiently improved in terms of rinsing properties. I couldn't say that.
On the other hand, alkylsulfonic acid anionic surfactants, nonionic surfactants or amphoteric surfactants do not generate metal scum and are frequently used as washing components for water. In the proposals using these surfactants, a specific surfactant is used, or various surfactants are used, and various ingredients are added to provide high detergency. , Which enhances its rinsability. As such an invention, a hard surface detergent composition containing a specific glycoside (Patent Document 2) and a nonionic detergent composition containing a specific nonionic surfactant (Patent Document 3) , A detergent composition comprising a specific cationic surfactant and an amino acid-based amphoteric surfactant (Patent Document 4), a specific nonionic surfactant, and a dishwashing liquid containing a specific fatty acid (salt) Cleaning composition (Patent Document 5), specific anionic surfactant, specific amphoteric surfactant, specific anionic surfactant, specific nonionic surfactant, and specific water-soluble dihydric alcohol There exists a cleaning composition (patent document 6) containing this.
Furthermore, although it is not intended for foam breakage, a liquid for kitchen use containing a cationic surfactant, a metal chelating agent, a water-soluble solvent, and a thickening polysaccharide as an object of improving the null thickness after washing. A cleaning composition (Patent Document 7) is known.
The present inventors use amphoteric surfactants that do not generate metal scum and develop soaps for developing hard surface foam detergents that have high detergency and good foaming properties. Considering that combined use with seeds and other components does not necessarily lead to improvement in rinsing properties, the goal was to establish a foam detergent formulation for hard surfaces that does not use soap. Amphoteric surfactants basically have good foaming and high detergency, but they are foamy even at low concentrations, so that their rinsing performance is not satisfactory. Accordingly, the present inventors have intensively studied combinations with other components with the aim of improving rinsing properties, and have completed the present invention.

JP 09-53092 A Japanese Patent Laid-Open No. 10-8090 JP 2002-180087 A JP 2002-121588 A JP 2004-203989 A Japanese Patent Laid-Open No. 2005-281539 Japanese Patent Laid-Open No. 10-204480

  The present invention provides an effective rinsing accelerator for improving the problem of rinsing of a detergent for hard surfaces containing a betaine type amphoteric surfactant that does not generate metal scum and does not contain soap. The purpose is to improve the practicality and usability of the hard surface cleaner.

In order to achieve the above object, the present invention has been found that the following configuration has an excellent effect.
(1), characterized in the early days containing a gemini quaternary ammonium salts, betaine type amphoteric surfactants accelerator rinse hard surface cleaners containing no soap contains.
(2) The rinse accelerator for a hard surface detergent according to (1), wherein the betaine-type amphoteric surfactant is an alkyl carbobetaine and / or an alkylamide carbobetaine .
(3) The hard surface as described in (1) or (2) above, wherein a mixing ratio of the gemini quaternary ammonium salt to the betaine amphoteric surfactant is 1/10 to 1/800 . A rinse aid for cleaning agents.
(4) The hard surface cleaning agent according to any one of (1) to (3), wherein the hard surface cleaning agent further contains a polyoxyethylene polyoxypropylene glycol-based surfactant . Rinsing accelerator.

In the present invention, as a cleaning component of the hard surface cleaning agent, a betaine amphoteric surfactant that does not generate metal scum, has high cleaning power, and has good foaming performance is used as a main cleaning component. In the present invention, the compound containing a quaternary ammonium salt as a rinsing accelerator is blended with this betaine-type amphoteric surfactant, so that the rinsing property is remarkably improved and both high detergency and high rinsing performance are achieved. The practicality and usability of the hard surface cleaner are extremely high.

Hereinafter, embodiments of the present invention will be specifically described.

The betaine-type amphoteric surfactant used in the present invention may be any of alkyl carbobetaine, alkylamido carbobetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidosulfobetaine, alkylamidohydroxysulfobetaine. Specific examples include lauryl-N, N-dimethylacetic acid betaine, laurylamidopropyl-N, N-dimethylacetic acid betaine, coconut alkylamidopropyl-N, N-dimethylhydroxypropylsulfobetaine, and the like.
In particular, alkylcarbobetaines typified by lauryl-N, N-dimethylacetic acid betaine and alkylamide carbobetaines exemplified by laurylamidopropyl-N, N-dimethylacetic acid betaine are preferred.
These betaine-type amphoteric surfactants are preferably blended in an amount of 0.1 to 10% by mass in consideration of the balance of foaming, detergency and rinsing properties.

Further, examples of the compound containing a quaternary ammonium salt used as a rinse accelerator in the present invention include dialkyl quaternary ammonium salts, benzalkonium quaternary ammonium salts, and gemini quaternary ammonium salts. Include didecyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride, 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide, etc. Is representative. Examples of the cationic polymer containing quaternary ammonium include RD-491 and RD-497 manufactured by Rhodia Nikka Co., Ltd.
Especially, the cationic polymer containing gemini type | mold quaternary ammonium salt and / or quaternary ammonium is excellent in the performance as a rinse promoter of the cleaning agent for hard surfaces of this invention.

In the present invention, the compound containing a quaternary ammonium salt as a rinse accelerator is preferably blended in a ratio of 1/10 to 1/800 with respect to the betaine amphoteric surfactant.
In Patent Document 1, the compounding ratio of the compound containing a quaternary ammonium salt and the betaine-type amphoteric surfactant is 9/1 to 1/9, whereas the former compounding amount is low in the present invention. However, it is considered that the presence of soap affects the high rinsing performance.
As a result of the study, it was confirmed that the compound containing a quaternary ammonium salt is effective only as a rinsing accelerator for betaine-type amphoteric surfactants and not effective for amino acid-based amphoteric surfactants. It was done.

In the present invention, in order to further improve rinsing properties, it is preferable that a polyoxyethylene polyoxypropylene glycol surfactant is further contained as a component of the hard surface cleaning agent.
Examples of polyoxyethylene polyoxypropylene glycol include pluronic manufactured by ADEKA Corporation, preferably having an ethylene oxide content of 50% or less, more preferably an ethylene oxide content of 20% or less. Specific examples thereof include Pluronic L61, Pluronic L71, Pluronic L101, Pluronic 25R-1, Pluronic 25R-2, and the like.

The hard surface cleaning agent used in the present invention includes an organic acid and / or a salt thereof, other types of surfactants, solvents, thickeners, perfumes, disinfectants, rust prevention, depending on the properties to be added. Agents, chelating agents, deodorants, water repellents, antifouling agents and the like may be appropriately blended.

Next, based on specific examples, the rinsing accelerator for the hard surface cleaning agent of the present invention will be described in more detail.
Prior to the examples, test methods in the examples will be described.

(1) Rinsability Easiness of rinsing means that foaming is good in the rinsing process after applying the cleaning composition to the hard surface, and foaming when diluted with rinsing water is involved. In other words, when the detergent composition is diluted with a certain amount of water, it is determined that the rinsing property is better as the amount of foaming decreases. Therefore, the amount of bubbles in a solution diluted to 0.1% with tap water should be measured. The rinsability was evaluated by
<Amount of foam>
30 mL (20 ° C.) of a detergent composition diluted to 0.1% with tap water is placed in a 100 mL stoppered graduated cylinder, shaken up and down 10 times by hand, and left still for 20 seconds. The remaining amount of foam (mL) after the lapse was measured. The smaller the remaining amount of foam in this test, the better the rinsing properties.

(2) Foaming when sprayed Filled with a detergent composition in a commercially available trigger spray container (trigger spray is made by Canyon Co., Ltd.) and sprayed from a distance of 20 cm toward the tile wall surface. Foaming was visually judged according to the following criteria.
A: Very well foamed and feel good.
○: Good foaming and good usability.
Δ: Slight foaming, but the feeling of use is not so good.
X: Almost no foaming and use feeling is not good.

(3) Detergency <model soap residue>
A soap scum fouling board in which a mixed solution of 10 parts of calcium stearate, 10 parts of ion-exchanged water and 80 parts of ethanol was evenly adhered to the surface of the black tile board, and then aged in a film by heating at about 200 ° C. for 1 hour. Was made.
<Detergency test>
A urethane sponge (4 cm × 9 cm × 3 cm) of a detergency tester was impregnated with 2 mL of the cleaning composition, and the scrub cleaning test was performed 10 times under a load of 600 g. Detergency is achieved by using a standard judgment dirt plate prepared in advance (10 judgment dirt boards are prepared with 10 being completely cleaned and 1 being no dirt). The degree of comparison was judged. The detergency was evaluated as 10 for ◎, 9-8 for ◯, 7-6 for Δ, and 5-1 for x.

(4) Rinsability practical test Spray the cleaning composition 15 times (approx. 10 mL injection) into a stainless steel bathtub of outside dimensions 900 mm (W) x 700 mm (D) x 600 mm (H) using a commercially available trigger spray container. After rubping the whole of the bathtub with a urethane sponge, it was washed with water in a shower, and the rinsing time until bubbles disappeared was measured. In addition, the amount of shower water at this time was about 12 L / min.

<Test 1>
Examples and Comparative Examples having the compositions shown in Table 1 were prepared and tested for rinsing properties (foam amount) and foaming when sprayed with a trigger spray.

When the quaternary ammonium salt is not blended as in Comparative Example 1, the remaining amount of foam in the rinsing test is large and the rinsing property is not good, whereas the benzalkonium type, dialkyl type, gemini type In Examples 1 to 6 in which a quaternary ammonium salt or a cationic polymer containing quaternary ammonium was blended, the remaining amount of foam was reduced, and rinsing was carried out by blending these quaternary ammonium salt and cationic polymer. Sex improvement effect was observed. Moreover, Examples 1-6 had good foaming when sprayed, and the feeling of use was also good.

<Test 2>
The influence of pH on the rinsing effect of the present invention was examined (Table 2). In Comparative Examples 2 to 5 in which the quaternary ammonium salt was not blended in the range of pH 3 to 11, the foam remaining amount was large, whereas in Examples 7 to 10 in which the quaternary ammonium salt was blended, the foam residue was clearly It is judged that the amount is decreased and the rinsing property is improved. The rinsing effect of the present invention is recognized in a wide pH range, and its usefulness is high.

<Test 3>
The influence of the quaternary ammonium salt addition concentration used in the present invention was examined. (Table 3)
The effect was recognized when the blending ratio of the quaternary ammonium salt to the betaine amphoteric surfactant was in the range of 1/10 to 1/800. (Examples 11 to 18)

<Test 4>
It was confirmed whether or not the rinsing promotion effect (foam reduction effect) of the quaternary ammonium salt was also found in surfactants other than the betaine amphoteric surfactant. (Table 4)
As seen in Comparative Examples 7 to 15, when an anionic surfactant, a nonionic surfactant, and an amino acid type amphoteric surfactant are used, no foam reduction effect is observed even when a quaternary ammonium salt is added. No rinsing promoting effect was observed. That is, only when a quaternary ammonium salt was added to the betaine type amphoteric surfactant, a foam reducing effect was observed, and a rinsing improvement effect could be confirmed.

<Test 5>
About the Example and comparative example which are shown in Table 5, the rinsing property test (foam remaining amount), the rinsing property practical test, the foaming when spraying with the trigger spray, and the detergency against the model soap residue were tested. From the results of Examples 20 to 23 and Comparative Examples 16 to 18, there is a correlation between the evaluation of the rinsing test (remaining amount of foam) employed in this example and the practical rinsing test, and the quaternary ammonium salt. The effect of blending was revealed. Furthermore, a synergistic effect between the quaternary ammonium salt and polyoxyethylene polyoxypropylene glycol was also confirmed. In Examples 20 and 22 in which a quaternary ammonium salt was blended in a rinsing practical test, the rinsing time was shortened by about 20% as compared with Comparative Examples 16 to 18 in which the quaternary ammonium salt was not blended. In Examples 21 and 23 blended with polyoxypropylene glycol, it was revealed that the length was shortened by about 30%. Moreover, Examples 20-23 confirmed that foaming was good when sprayed, there was also a feeling of use, and the detergency was also good.

The rinsing accelerator for the hard surface cleaning agent of the present invention can be used for a wide range of cleaning purposes.

Claims (4)

Characterized the early days containing a gemini quaternary ammonium salts, betaine type amphoteric surfactants accelerator rinse hard surface cleaners containing no soap contains. The rinsing accelerator for a hard surface cleaning agent according to claim 1, wherein the betaine-type amphoteric surfactant is an alkyl carbobetaine and / or an alkylamide carbobetaine . The promotion of rinsing of the hard surface cleaning agent according to claim 1 or 2, wherein a mixing ratio of the gemini type quaternary ammonium salt to the betaine type amphoteric surfactant is 1/10 to 1/800. Agent. The rinsing accelerator for a hard surface cleaning agent according to any one of claims 1 to 3, wherein the hard surface cleaning agent further contains a polyoxyethylene polyoxypropylene glycol surfactant .