JP6654353B2 - Hard surface cleaning composition and method for cleaning hard surface - Google Patents

Description

  The present invention relates to a hard surface cleaning composition suitable for cleaning hard surfaces such as tableware, bathtubs, tile walls and the like made of glass, ceramics, metals, plastics and the like, and a method for cleaning hard surfaces using the cleaning composition. About.

  In a humid environment such as in a bathroom, washroom, kitchen, toilet, etc. or in an automatic dishwasher cabinet, microorganisms can easily propagate and generate slime called biofilm such as pink microbial stains. It's easy to do. As a detergent that can prevent the generation of biofilms such as pink scum on hard surfaces and can be removed by washing, a detergent containing specific cationic surfactants, amphoteric surfactants, and organic compounds such as benzyl alcohol in a specific range. (Patent Document 1), a cleaning agent containing a specific ratio of an alkali metal hypochlorite, an alkali metal hydroxide, and a surfactant (Patent Document 2), a quaternary ammonium salt, and N, N-bis ( Detergents containing an alkylamine such as (3-aminopropyl) dodecylamine and alkylpropylamine (Patent Document 3) are known.

JP 2012-255073 A JP 2005-75873 A JP 2007-224298 A

The detergent containing a cationic surfactant described in Patent Literature 1 is a detergent for an automatic dishwasher because the cationic surfactant is easily adsorbed on a hard surface and remains easily, and has a low foam suppressing property. There was a problem that it was difficult to use. Further, in the cleaning agent containing an alkali metal hypochlorite described in Patent Document 2, the effect of hypochlorite is inactivated by dirt, or becomes unstable due to the coexisting alkali metal hydroxide. There was a possibility that the biofilm removal effect was reduced. Particularly, in the case of a detergent for a commercial dishwasher used under highly alkaline conditions, there is a problem that the stability of hypochlorite is reduced and the biofilm removing effect is significantly reduced.
In addition, a chelating agent is often added to the hard surface cleaner, but hypochlorite has a problem in stability in the presence of the chelating agent.

  Further, since the cleaning agent described in Patent Document 3 contains a quaternary ammonium salt which is a cationic surfactant, there is a possibility that the quaternary ammonium salt may remain adsorbed on a hard surface, and a low foam suppressing property. Therefore, when used as a cleaning agent for an automatic dishwasher, particularly for a commercial automatic dishwasher having a large stirring power, there is a problem that foaming may hinder the washing operation. Further, in the detergent described in Patent Document 3, the alkaline component is an alkylamine such as N, N-bis (3-aminopropyl) dodecylamine or alkylpropylamine, and the pH as a concentrate is 8.5 to 9.2. However, the pH at the time of diluting and washing is even lower, so that the washing property against protein stains and oil stains is not sufficient. For this reason, it did not exhibit sufficient washing performance as a detergent for automatic dishwashers, particularly for commercial automatic dishwashers.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems of the prior art, and as a result, N- (3-aminopropyl))-N-alkylpropane-1, which has been conventionally used as a disinfectant for Legionella bacteria and the like. Of N- (3-aminopropyl) -N-alkylpropane-1,3-diamine against microorganisms by using, 3-diamine in combination with an alkali compound selected from alkali metal hydroxides and silicates In addition to the action, N- (3-aminopropyl))-N-alkylpropane-1,3-diamine and a specific alkali compound act synergistically to effectively wash and remove protein stains and oil stains. And completed the present invention.

式中、Ｒは少なくとも４個の炭素原子を含む直鎖状又は分岐状アルキル鎖である。
（２）（Ａ）成分を１００質量部に対し、（Ｂ）成分を１〜６００００質量部含有する上記（１）の硬質表面洗浄剤組成物、
（３）（Ｄ）成分の消泡剤が非イオン系界面活性剤、シリコーン系消泡剤、アルコール系消泡剤から選ばれる１種以上である上記（１）又は（２）の硬質表面洗浄剤組成物、
（４）（Ｅ）成分が、２−エチルヘキサン酸及び／又はその塩、カプリル酸及び／又はその塩、アルケニルスルホコハク酸及び／又はその塩、メタキシレンスルホン酸及び／又はその塩、アルキル基の炭素数がＣ６〜１０のアルキルポリグルコシド、オクチルアミンオキサイド、デシルジメチルアミンオキサイドから選ばれる１種以上である上記（１）〜（３）のいずれかの硬質表面洗浄剤組成物、
（５）（Ｆ）成分として、キレート剤を（Ａ）成分１００質量部に対し１〜６００００質量部含有する上記（１）〜（４）のいずれかの硬質表面洗浄剤組成物、
（６）（Ｇ）成分として、高分子ポリマー系分散剤を（Ａ）成分１００質量部に対し０．０３〜４００００質量部含有する上記（１）〜（５）のいずれかの硬質表面洗浄剤組成物、
（７）硬質表面洗浄剤組成物が、自動食器洗浄機用である上記（１）〜（６）のいずれかの硬質表面洗浄剤組成物、
（８）上記（１）〜（７）のいずれかに記載の硬質表面洗浄剤組成物を、（Ａ）成分濃度０．００００５％〜２％、ｐＨ９．０〜１３．５溶液として洗浄する硬質表面の洗浄方法、
を要旨とするものである。
That is, the present invention provides (1) an amine compound represented by the following formula (1) as a component (A), an alkali compound selected from alkali metal hydroxides and silicates as a component (B), and water as a component (C). , Containing a defoamer as a component (D) and a solubilizer as a component (E),
The component (D) is contained in an amount of 100 to 15,000 parts by mass with respect to 100 parts by mass of the component (A), and
A hard surface cleaning composition comprising the component (E) in an amount of 600 to 20,000 parts by mass with respect to 100 parts by mass of the component (A).

Wherein R is a straight or branched alkyl chain containing at least 4 carbon atoms.
(2) The hard surface cleaning composition according to the above (1), which contains the component (B) in an amount of 1 to 60,000 parts by mass with respect to 100 parts by mass of the component (A).
(3) The hard surface cleaning according to the above (1) or (2), wherein the defoaming agent of the component (D) is at least one selected from a nonionic surfactant, a silicone defoaming agent and an alcohol defoaming agent. Agent composition,
(4) The component (E) is 2-ethylhexanoic acid and / or a salt thereof, caprylic acid and / or a salt thereof, alkenylsulfosuccinic acid and / or a salt thereof, meta-xylene sulfonic acid and / or a salt thereof, and an alkyl group The hard surface cleaning composition according to any one of (1) to (3), wherein the composition is at least one selected from alkyl polyglucosides having 6 to 10 carbon atoms, octylamine oxide, and decyldimethylamine oxide.
(5) The hard surface cleaning composition according to any one of the above (1) to (4), which contains 1 to 60,000 parts by mass of a chelating agent as component (F) based on 100 parts by mass of component (A).
(6) The hard surface cleaner according to any one of the above (1) to (5), which contains 0.03 to 40000 parts by mass of a polymer dispersant as component (G) based on 100 parts by mass of component (A). Composition,
(7) The hard surface cleaning composition according to any one of (1) to (6) above, wherein the hard surface cleaning composition is for an automatic dishwasher.
(8) The hard surface cleaning composition according to any one of the above (1) to (7), wherein the hard surface cleaning composition is a (A) solution having a component concentration of 0.00005% to 2% and a pH of 9.0 to 13.5. Surface cleaning method,
It is the gist.

  The hard surface cleaning composition of the present invention uses a combination of an alkali compound selected from alkali metal hydroxides and silicates and N- (3-aminopropyl) alkylamine to provide a hard surface protein. Dirt and oil stains can be effectively washed and removed, and a stable and excellent biofilm suppression effect is exhibited even when an alkali compound is present.

  Examples of the amine compound as the component (A) in the cleaning composition of the present invention include those having a linear alkyl group having 4 or more carbon atoms and a branched alkyl group in the alkyl group. Numbers 4 to 18 are preferable, and in particular, N- (3-aminopropyl) -N-butylpropane-1,3-diamine having 4 carbon atoms in the alkyl group represented by CAS No. 1555-68-6, CAS No. 85938 N- (3-aminopropyl) -N-decylpropane-1,3-diamine having 10 carbon atoms in the alkyl group represented by -54-1, and 12 carbon atoms in the alkyl group represented by CAS No. 2372-82-9. N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine, (Z) -N- (3-amino having 18 carbon atoms in the alkyl group which is CAS No. 28872-1-01-7 Propyl) -N'-9-octadecenylpropane-1,3-diamine, wherein the alkyl group of CAS No. 61791-57-9 is N- (3-aminopropyl) -N-alkylpropane- derived from tallow 1,3-Diamine is more preferred, and N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine having 12 carbon atoms in the alkyl group is most preferred from the viewpoint of versatility. Here, as the ratio of the fatty acid composition of beef tallow, for example, myristic acid is 2.0%, palmitic acid is 32.5%, stearic acid is 14.5%, oleic acid is 48.3%, and linoleic acid is 2%. 0.7%, but is not limited to this.

  Examples of the alkali compound as the component (B) include alkali metal hydroxides and silicates. Examples of the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, potassium orthosilicate, sodium orthosilicate, sodium sesquisilicate, potassium sesquisilicate, sodium metasilicate, potassium metasilicate, and No. 1 specified in JIS K1408. Examples include sodium silicate, No. 1 potassium silicate, No. 2 sodium silicate, No. 2 potassium silicate, No. 3 sodium silicate, No. 3 potassium silicate, and the like, with potassium hydroxide and sodium hydroxide being preferred.

  The hard surface cleaning composition of the present invention preferably contains 1 to 60,000 parts by mass of the component (B) based on 100 parts by mass of the component (A). )) The component is more preferably contained in an amount of 10 to 10,000 parts by mass, more preferably 100 to 5000 parts by mass, and most preferably 300 to 3000 parts by mass. If the proportion of the component (B) per 100 parts by mass of the component (A) is less than 1 part by mass, the cleaning properties may be poor, and if it exceeds 60000 parts by mass, the storage stability may be reduced.

  Examples of the water as the component (C) include purified water, distilled water, ion-exchanged water, soft water, pure water, ultrapure water, and tap water. These may be used alone or in combination of two or more. Among them, water in which hardness components such as calcium and magnesium which are present in trace amounts in water and heavy metals such as iron are removed is preferable, and ion exchange water is most preferable in terms of economy and storage stability.

  It is preferable that the hard surface cleaning composition of the present invention further contains an antifoaming agent as the component (D). The component (A) in the hard surface cleaning composition of the present invention has a lower foaming property than a cationic surfactant, but when a defoaming agent is added, the foaming property is further suppressed, and especially for business use having a strong stirring power. Even when used as a cleaning agent for a dishwasher, there is no possibility of causing a problem due to foaming. Examples of the antifoaming agent include a nonionic surfactant, a silicone-based antifoaming agent, and an alcohol-based antifoaming agent, and one or more of these antifoaming agents can be used in combination. As the nonionic surfactant, for example, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene dialkyl ether, polyoxyethylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, pluronic block polymer, tetronic block polymer, Examples include reverse pluronic block polymers, reverse stetronic block polymers, diethylene glycol laurate, glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, and natural waxes. Among the nonionic surfactants, polyoxyethylene polyoxypropylene alkyl ether represented by the following formula (2) is particularly preferable.

(Formula 2)
RO- (EO) m (PO) n-R '(2)
(Wherein, R represents a linear or branched alkyl group having an average of 8 to 20 carbon atoms, R ′ represents a hydrogen atom or a methyl group, EO represents an additional unit of ethylene oxide, and PO represents an additional unit of propylene oxide. m is 2.0 to 20.0, n is 0.4 to 20.0, and the additional unit ratio m / n of EO / PO is 0.6 to 5.0.

  Among the polyoxyethylene polyoxypropylene alkyl ethers, m in the above formula (2) is 3 to 6, n is 4 to 8, and the EO / PO addition unit ratio m / n is 0.8 to 2.0. Some are more preferable in terms of detergency and storage stability.

  Examples of the silicone-based antifoaming agent include dimethyl silicone oil, silicone oil compound, silicone emulsion, polyether-modified polysiloxane, and fluorosilicone oil. Examples of the alcohol-based antifoaming agent include octyl alcohol, acetylene alcohol and the like. The antifoaming agent of the component (D) is preferably compounded in an amount of 0.3 to 15,000 parts by mass, more preferably 20 to 5,000 parts by mass, and more preferably 50 to 3,000 parts by mass, per 100 parts by mass of the component (A). More preferably, it is more preferably 100 to 2,000 parts by mass. If the ratio of the defoaming agent per 100 parts by mass of the component (A) is less than 0.3 part by mass, the defoaming property may not be obtained, and if it exceeds 15,000 parts by mass, (D) There is a possibility that the components may remain, resulting in poor rinsing.

  The hard surface cleaning composition of the present invention preferably further contains a solubilizer as the component (E). Examples of the solubilizer include 2-ethylhexanoic acid and / or a salt thereof, caprylic acid and / or a salt thereof, alkenylsulfosuccinic acid and / or a salt thereof, metaxylenesulfonic acid and / or a salt thereof, and a carbon number of an alkyl group. C6-10 alkyl polyglucoside, octylamine oxide, decyldimethylamine oxide and the like. The component (A) is unstable under a high alkali having a high component (B) concentration (about 20% by mass or more of sodium hydroxide), but when a solubilizing agent is used in combination, the stability of the component (A) under a strong alkali Can be further enhanced. In particular, when the chelating agent of the component (F) is used in combination, the stability may be deteriorated. However, the stability of the component (A) can be increased even when the chelating agent is used in combination by adding a solubilizing agent. Among these solubilizers, 2-ethylhexanoic acid and / or a salt thereof, octylic acid and / or a salt thereof, meta-xylene sulfonic acid and / or a salt thereof are preferable, and sodium 2-ethylhexanoate and 2-ethylhexanoate are particularly preferable. Potassium hexanoate is preferred. The solubilizing agent of the component (E) is preferably blended in an amount of 10 to 30,000 parts by mass, more preferably 30 to 4000 parts by mass, per 100 parts by mass of the component (A). When the detergent composition contains the defoamer of the component (D), the storage stability of the detergent composition may be reduced. Therefore, the ratio of the solubilizing agent of the component (E) is 100%. It is preferably from 30 to 20,000 parts by mass, more preferably from 50 to 8000 parts by mass, further preferably from 100 to 5,000 parts by mass, most preferably from 200 to 3,000 parts by mass, per part by mass. Further, when the detergent composition contains the component (F), the storage stability of the detergent composition may be reduced. Therefore, the solubilizing agent of the component (E) is added to 100 parts by mass of the component (A). The amount is preferably from 20 to 6000 parts by mass, more preferably from 50 to 600 parts by mass. Furthermore, when the component (D) and the component (F) are contained, the proportion of the component (E) is preferably 50 to 30,000 parts by mass, more preferably 100 to 8,000 parts by mass, per 100 parts by mass of the component (A). , 300 to 5,000 parts by mass.

  The hard surface cleaning composition of the present invention may further contain a chelating agent as the component (F). Examples of chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, tripolyphosphoric acid, glutamic acid diacetate, methylglycine diacetate, gluconic acid, orthophosphoric acid, pyrophosphoric acid, hexametaphosphoric acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminopentaacetic acid, and triethylenetriaminopentaacetic acid. Ethylenetetraamine hexaacetic acid, hydroxyethyl iminodiacetic acid, dihydroxyethylglycine, aspartic diacetate, β-alanine diacetate, serine diacetate, glycolic acid, lactic acid, citric acid, tartaric acid, malic acid and alkali metal salts thereof And alkanolamine salts such as ammonium salt, monoethanolamine, triethanolamine and monoisopropanolamine. Among these, ethylenediaminetetraacetate, nitrilotriacetate, glutamic acid diacetate, and methylglycine diacetate are preferred from the viewpoint of detergency and biofilm suppression, and particularly preferred is ethylenediaminetetraacetate sodium. These may be used alone or in combination of two or more. From the viewpoint of biofilm inhibition, the chelating agent is preferably 1 to 60,000 parts by mass, more preferably 20 to 20,000 parts by mass, and still more preferably 50 to 6,000 parts by mass, based on 100 parts by mass of the component (A). It is most preferable to mix 100 to 4000 parts by mass.

  The hard surface cleaning composition of the present invention can further contain a polymer dispersant as the component (G), and especially when the chelating agent of the component (F) is added, the cleaning properties and the prevention of scale adhesion can be improved. The performance is improved. The compounding amount of the polymer dispersant is preferably 0.03 to 40000 parts by mass, more preferably 5 to 2,000 parts by mass, and more preferably 20 to 800 parts by mass with respect to 100 parts by mass of the component (A). preferable. Examples of the polymer dispersant include at least one selected from polycarboxylic acid type polymers, sulfonic acid type polymers, and salts thereof. Examples of the polycarboxylic acid type polymer include polyacrylic acid, polymaleic acid, polymethacrylic acid, acrylic acid type copolymer, maleic acid type copolymer, methacrylic acid type copolymer, and the like. Acid-maleic acid copolymers are more preferred. The weight average molecular weight of polyacrylic acid is preferably from 1,000 to 20,000, particularly preferably from 2,000 to 15,000. If the weight average molecular weight is less than 1,000, it is not preferable in terms of scale prevention, and if it exceeds 20,000, it is not preferable in terms of storage stability. Examples of the sulfonic acid type polymer include an acrylic acid-sulfonic acid type monomer copolymer, and the weight average molecular weight of the acrylic acid-sulfonic acid type monomer copolymer is preferably from 1,000 to 20,000, particularly preferably 2 to 20,000. 5,000 to 15,000. If the weight average molecular weight is less than 1,000, it is not preferable in terms of scale prevention, and if it exceeds 20,000, it is not preferable in terms of storage stability. As the salt of the polycarboxylic acid type polymer or the sulfonic acid type polymer used as the polymer dispersant, alkali metal salts such as sodium and potassium are preferable.

  The hard surface cleaning composition of the present invention may further contain components commonly used in the art. Examples of such components include a water-soluble solvent, a pH adjuster, a thickener, a fragrance, a dye, and the like.

  Examples of the water-soluble solvent include alcohol solvents, glycol ether solvents, and the like. Examples of the alcohol solvents include ethyl alcohol, isopropanol, 3-methoxybutanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and propylene glycol. , Dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, glycerin and the like.

  Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol. Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether Ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, etc. Is mentioned.

  Examples of the pH adjuster include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium citrate, sodium hydrogen citrate, sodium phosphate, And sodium hydrogen phosphate.

  Examples of the thickener include sorbitol, glycerin, propylene glycol, pentylene glycol, hexylene glycol, octylene glycol, xylitol, erythritol, polyethylene glycol having an average molecular weight of 200 to 6,000, ethylene glycol, 1,3- Butylene glycol, polyhydric alcohols such as reduced starch saccharified products, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylmethylcellulose, alginic acid derivatives such as sodium alginate, fatty acid derivatives such as stearyl alcohol and a kind of mucopolysaccharide. Certain hyaluronic acid derivatives, chondroitin sulfate derivatives, and the like.

  Examples of the fragrance include natural fragrances, synthetic fragrances, and compounded fragrances. Examples of the dye include natural dyes, synthetic dyes, and mixtures thereof.

  When the hard surface is cleaned with the hard surface cleaning composition of the present invention, it is used as a solution having a component concentration of 0.00005% by mass to 2% by mass and a pH of 9.0 to 13.5. Preferably, the component (A) has a concentration of 0.0001 to 1% by mass and pH 9.3 to 12.8, and more preferably the component (A) has a concentration of 0.0005 to 0.05% by mass and pH 9.5 to 12.2. Used as The washing temperature is preferably from 30 to 90 ° C, more preferably from 40 to 70 ° C.

  The hard surface cleaning composition of the present invention is suitable for cleaning the surface of any hard material such as aluminum, stainless steel, silver or other metal, melamine, plastic, glass, porcelain, lacquerware, and ceramics. . The hard surface cleaning composition of the present invention can be used for general households such as kitchen ventilation fans and gas ranges, bath kettles, toilets, tableware, vehicles, and buildings, and hard materials such as metals, plastics, glass, ceramics, and concrete. And the like, but is suitable as a detergent for dishwashers. Commercial dishwashers with limited operating conditions compared to home dishwashers, such as automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, etc. It is suitable as a cleaning agent for cleaning, and has excellent cleaning effects, foam suppressing properties, and biofilm suppressing ability as compared with conventional cleaning agents for commercial automatic dishwashers.

Hereinafter, the present invention will be described specifically with reference to Examples. In the following examples, “%” is based on mass unless otherwise specified.
The compounds used in the test are described below. The number in parentheses after the alcohol is the number of carbon atoms in the aliphatic alcohol, EO is an abbreviation for ethylene oxide, and PO is an abbreviation for propylene oxide, and the numbers after the numbers indicate the number of moles of EO and PO added, respectively. In addition, the numerical value of the combination of the example and the comparative example in the table represents the mass% of the pure content.

Amine compound A-1: N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine A-2: N- (3-aminopropyl) -N-butylpropane-1,3-diamine A- 3: N- (3-aminopropyl) -N-decylpropane-1,3-diamine A-4: N- (3-aminopropyl) -N-octadecenylpropane-1,3-diamine A-5 : N- (3-aminopropyl) -N-alkylpropane-1,3-diamine (provided that the alkyl group is derived from tallow)

Alkali compound B-1: sodium hydroxide B-2: potassium hydroxide B-3: sodium silicate (39% pure, molar ratio SiO2: Na2O = 3: 1) Trade name: Sodium silicate No. 3, manufactured by ADEKA Corporation B-4: Potassium silicate (40% pure, molar ratio SiO2: K2O = 3: 1) Trade name: Potassium A silicate, manufactured by Nippon Chemical Industry Co., Ltd.

Water C-1: ion exchange water

Antifoaming agent D-1: 5 mol of EO of dodecyl alcohol, 5 mol of PO adduct D-2: 4 mol of EO of undecyl alcohol, 7 mol of adduct of PO D-3: 12 mol of EO of tetradecyl alcohol, 16 mol of PO adduct D-4 : Adduct of dodecyl alcohol with 10 mol of EO and 12 mol of PO D-5: Pluronic nonionic surfactant Trade name: Adecapluronic 25R-1, manufactured by ADEKA Corporation (block adduct of 3 mol of PO, 43 mol of EO and 3 mol of PO)
D-6: Silicone resin Product name: KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.

Solubilizer E-1: Sodium 2-ethylhexanoate E-2: Potassium caprylate E-3: Sodium meta-xylene sulfonate E-4: Hexylglucoside Trade name: AG6206, E- manufactured by Lion Specialty Chemicals Co., Ltd. 5: 2-Ethylhexyl glucoside Trade name: AG6202, manufactured by Lion Specialty Chemicals Co., Ltd. E-6: octyldimethylamine oxide E-7: decyldimethylamine oxide

Chelating agent F-1: Sodium ethylenediaminetetraacetate F-2: Sodium nitrilotriacetate F-3: Sodium methylglycine diacetate F-4: Sodium glutamic acid diacetate

Polymer Dispersant G-1: Sodium polyacrylate (weight average molecular weight is 4,000)
G-2: sodium polyacrylate (weight average molecular weight is 15,000)
G-3: Acrylic acid-maleic acid copolymer (weight average molecular weight 10,000)

Examples 1 to 80, Comparative Examples 1 to 10
Hard surface cleaning compositions were prepared based on the formulations shown in Tables 1-9. In addition, for each detergent composition or a diluted product thereof, the following methods are used to show the biofilm inhibitory property (stained, no stain), washability (protein stain), and storage stability (−5 ° C., 25 ° C., 40 ° C.). Was measured. The results are shown in Tables 1 to 9.

* 1: Biofilm prevention test <Test method>
5 g of each detergent composition was added to a sterilized Mueller Hinton medium [manufactured by Nippon Becton Dickinson Co., Ltd.] to make the total amount 100 g, and a 5% by mass conc solution of each detergent composition was prepared. This conch solution was further diluted using a sterilized Mueller Hinton medium to a concentration of 0.1% by mass as a detergent composition, and 2 mL each was weighed into a 24-well microplate (manufactured by Asahi Techno Glass Co., Ltd.). Was. Further, as a stain component when there is a soil load, 3% by mass of bovine albumin was prepared as a conc solution and added to a 24-well microplate so as to be 0.3% by mass.
Pseudomonas aeruginosa NBRC13275 and Klebsiella pneumoniae ATCC13883 were each pre-cultured at 37 ° C. for 18 hours using an LB medium (manufactured by Becton Dickinson Japan) using Pipetteman. And used to inoculate 100 μL of the test solution in the microplate. This was cultured at 37 ° C. for 48 hours, and the culture solution was discarded. The biofilm attached to the microplate wall was stained with a 0.1% by mass crystal violet solution, rinsed with sterilized water, and then visually inspected for the state of biofilm formation. The film inhibition was evaluated according to the following criteria.
<Evaluation criteria>
◎: Biofilm covers 0 to less than 20% of the plate wall surface.
：: Biofilm covers 20% or more and less than 40% of the plate wall surface.
Δ: Biofilm covers 40% or more and less than 60% of the plate wall surface.
×: A state in which the biofilm covers 60% or more of the plate wall surface.
△, 、, and ◎ were judged to be practical.

* 2: Detergency test Detergency was evaluated by washing the object under the following conditions.
<Washing conditions>
Washing machine used: HOBART automatic dishwasher (model AM-14)
Washing temperature: 66 ° C
Washing time: 40 seconds Rinse temperature: 82 ° C
Rinse time: 9 seconds Washing liquid: 0.07% by mass dilution of the detergent composition Water used: Hard water of 200 mg / L [German hardness 11.2 ° DH] in terms of calcium carbonate <Preparation of washing object>
A 5% by mass egg yolk solution was uniformly applied to a white porcelain dish (diameter 12 cm), heated at 100 ° C. for 30 minutes, and denatured to obtain a washing object for a detergency test.
<Evaluation method>
The 10 contaminated dishes prepared by the above method were placed in a washing rack of an automatic dishwasher, washed under the above washing conditions, rinsed, and then dried at room temperature. After drying, a 0.1% amide black solution was sprinkled on the entire dish, and the area (S ₁ ) of the colored portion that was colored was measured. From the initial contaminated area (S ₀ ), the cleaning rate was determined by the following equation, and the average value of 10 dishes was adopted as the result.

(Equation 1)
Cleaning rate (%) = {(S ₀ −S ₁ ) / S ₀ } × 100

<Evaluation criteria>
A: The cleaning rate is 80% or more.
：: The cleaning rate is 60% or more and less than 80%.
Δ: The cleaning rate is 40% or more and less than 60%.
X: The cleaning rate is less than 40%.
△, 、, and ◎ were judged to be practical.

* 3: Suppressing property test Suppressing property was tested and evaluated under the following conditions.
<Test conditions>
Washing machine used: Automatic dishwasher manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd. (Model JWD-6)
Washing liquid temperature: 60 ° C
Detergent concentration: 0.1% by weight
Soil condition: A test was conducted with and without the addition of a composite stain to the cleaning liquid so as to have a concentration of 5% by weight. (The composite soil was rice starch: egg yolk: tallow = 1: 2: 4)
Water used: Water with a hardness of 5 ° DH (adjusted with calcium chloride)
<Evaluation Method of Foam Suppressing Property> Under the above test conditions, the washing process of the washing machine was continuously operated for 10 minutes, and foaming two minutes after immediately opening the lid of the automatic dishwashing machine was subjected to a sensory evaluation based on a criterion.
<Evaluation criteria>
◎: Less bubbles.
：: Some bubbles are formed.
Δ: Foamed, but no practical problem.
×: Very foamy.
△, 、, and ◎ were judged to be practical.

* 4: Storage stability test <Test method>
100 g of each detergent composition was placed in a transparent glass bottle, and allowed to stand at -5 ° C, 25 ° C, and 40 ° C for one month, and the appearance was observed.
<Evaluation criteria>
：: stable without any separation or turbidity.
Δ: There is no overall separation, but slight turbidity is observed.
X: Separation or turbidity is observed.
△ and ○ were judged to be practical.

Claims (8)

As the component (A), an amine compound represented by the following formula (1), as the component (B), an alkali compound selected from alkali metal hydroxides and silicates, as the component (C), water, and as the component (D), Containing a foaming agent and a solubilizer as a component (E);
The component (D) is contained in an amount of 100 to 15,000 parts by mass with respect to 100 parts by mass of the component (A), and
A hard surface cleaning composition comprising the component (E) in an amount of 600 to 20,000 parts by mass per 100 parts by mass of the component (A).

Wherein R is a straight or branched alkyl chain containing at least 4 carbon atoms. The hard surface cleaning composition according to claim 1, wherein the component (B) is contained in an amount of 1 to 60000 parts by mass with respect to 100 parts by mass of the component (A). The hard surface cleaning composition according to claim 1 or 2, wherein the defoaming agent of the component (D) is at least one selected from a nonionic surfactant, a silicone defoaming agent, and an alcohol defoaming agent. The component (E) is 2-ethylhexanoic acid and / or a salt thereof, caprylic acid and / or a salt thereof, alkenylsulfosuccinic acid and / or a salt thereof, metaxylenesulfonic acid and / or a salt thereof, and an alkyl group having a carbon number of The hard surface cleaning composition according to any one of claims 1 to 3, which is at least one selected from C6 to C10 alkyl polyglucosides, octylamine oxide, and decyldimethylamine oxide. The hard surface cleaning composition according to any one of claims 1 to 4, wherein the composition further comprises 1 to 60,000 parts by mass of a chelating agent as component (F) based on 100 parts by mass of component (A). The hard surface cleaning composition according to any one of claims 1 to 5, wherein a high-molecular polymer-based dispersant is contained as the component (G) in an amount of 0.03 to 40000 parts by mass based on 100 parts by mass of the component (A). The hard surface cleaning composition according to any one of claims 1 to 6, wherein the hard surface cleaning composition is for an automatic dishwasher. A method for cleaning a hard surface, comprising cleaning the hard surface cleaning composition according to any one of claims 1 to 7 as a solution having a component (A) concentration of 0.00005% to 2% and a pH of 9.0 to 13.5.