JPH0873890A - Liquid detergent composition for hard surface cleaning - Google Patents

Abstract

PURPOSE: To obtain the subject composition having an excellent detergency for an oily soil and soil redeposition prevention effects and capable of further improving the finish of subjects to be cleaned such as tablewares and glasses. CONSTITUTION: This liquid detergent composition for hard surface cleaning is obtained by containing 0.5-30wt.% alkaline agent, 0.1-20wt.% ionic surfactant represented by the following general formula (1), 0.5-20wt.% one or more of a liquid property improving agent selected from an aromatic carboxylic acid, an aromatic sulfonic acid and their salts, an alkylsulfate ester salt and a polyoxyethylene alkyl ethersulfate ester salt and a metallic ion trapping agent such as a copolymer obtained from maleic acid or maleic anhydride and a monomre coplymerizable therewith. R1 O(EO)m(PO)nR2 ...(1) [R1 is an alkyl, an alkenyl or an alkylphenyl group. R2 is hydrogen, an alkyl, an alkenyl or an alkylphenyl group. EO is an adding unit of ethylene oxide. PO is an adding unit of propylene oxide. (m) and (n) are each 0-10].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can easily remove any dirt adhering to a hard surface such as metal, glass, ceramics, plastics, etc. The present invention relates to a liquid hard surface cleaner composition having excellent liquid properties and suitable for cleaning using a cleaning machine.

[0002]

2. Description of the Related Art In recent years, from the viewpoints of labor shortage, maintenance of working environment, enhancement of hygiene management, etc., dishwashing in hotels, restaurants, lunch centers and the like has been automated by washing machines. In addition, mechanization and automation are rapidly spreading in the cleaning of parts and facilities of processing plants for meat, marine products and agricultural products, manufacturing plants for dairy products, beverages, etc., and cleaning of containers used in the food distribution field. There is.

Particularly in the field of dishwashing, menus are diversifying with changes in lifestyle and westernization of eating habits, and oil stains and protein stains tend to be attached. In addition, tableware with gold patterns and high-end items such as crystal glasses are increasingly used.

Conventionally, when cleaning these items by hand,
Detergents based on anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants or mixtures thereof have been used.

Although these cleaning agents are excellent in cleaning ability and foaming property, when used in a cleaning machine, a large amount of bubbles are generated in the pump for supplying the cleaning liquid, which hinders the operation of the pump. In addition, there is a problem that the spraying force on the object to be washed is weakened and the sufficient cleaning ability is not exhibited. In consideration of such problems, cleaning agents for washing machines were developed,
Mainly aimed at cleaning and removing oil stains are solid detergents composed of caustic alkali and water-soluble glycol ether (JP-A-61-296097), solid detergents composed of caustic alkali and water-soluble alkanolamine (JP 61-296098).

[0006] Further, as the one whose main purpose is the cleaning ability of the surfactant, there is a cleaning agent composed of a nonionic surfactant (JP-A-62-50397, JP-B-2-33760) and the like.

Furthermore, a liquid detergent comprising triporiphosphate, silicate, potassium hydroxide, hypochlorite, and water, which mainly focuses on chelating ability and washing ability of polyvalent metal ions (JP-A-62- No. 50399), a caustic alkali, sodium tripolyphosphate, a silicate, a detergent containing a polymer (Japanese Patent Laid-Open No. 63-37838), a detergent comprising caustic alkali and 2-hydroxyethyliminodiacetic acid salt, etc. From a composition (Japanese Patent Publication No. 2-27397), a detergent composition comprising a caustic alkali and an alkali metal salt of nitrilotriacetic acid, etc. (Japanese Patent Publication No. 3-60358), caustic alkali, polyacrylate and specific water A cleaning agent for an automatic dishwasher (JP-A-4-15299) has been reported.

[0008] However, these methods cannot easily remove food-derived contaminants adhering to tableware with a washing machine, and stains once dropped adhere to tableware and glasses to be whitened or wet. There are problems such as sticking.

In order to solve the above problems, the cleaning composition for an automatic dishwashing machine comprising a nonionic surfactant, a chelating agent and an enzyme (with a special focus on cleaning ability and calcium capturing ability) Techniques such as Kaihei 4-72398, JP-A-4-72397, and JP-A-4-72398) have been reported. However, even if these cleaning agents are used, the cleaning ability is insufficient, foaming causes a hindrance to the operation of the cleaning machine, and in the strong alkaline agent coexisting system, the strong electrolyte becomes a concentrated solution, so Agent,
The water of hydration necessary for dissolving the other components is deprived and precipitated, and it is very difficult to obtain a uniform high-concentration liquid detergent.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a cleaning agent capable of easily removing various stains attached to a hard surface such as metal, glass, ceramics and plastics. In particular, the present invention provides a liquid hard surface cleaner composition having excellent detergency against oil stains and an effect of preventing recontamination, and having good liquidity suitable for cleaning using a cleaning machine.

[0011]

The hard surface liquid detergent composition of the present invention is characterized by containing the following components (a), (b) and (c) or further component (d). (A) Alkaline agent: 0.5 to 30% by weight. (B) Surfactant represented by the following general formula (1): 0.1 to 20% by weight.

[0012]

Embedded image R ₁ O (EO) m (PO) nR ₂ ... (1) (R ₁ : a linear or branched alkyl group, alkenyl group or alkylphenyl group having 6 to 24 carbon atoms R ₂ : hydrogen or carbon Number 1 to 8 linear or branched alkyl group, alkenyl group or alkylphenyl group EO: Addition unit of ethylene oxide PO: Addition unit of propylene oxide m, n: 0 to 10 and not both 0 and m + n When adding EO or PO with a numerical value of 1 or more, random addition or block addition may be performed.
The order of adding O and PO does not matter. )

(C) One or more kinds of liquidity improvers selected from aromatic carboxylic acids, aromatic sulfonic acids and salts thereof, alkyl sulfate ester salts and polyoxyethylene alkyl ether sulfate ester salts: 0.5 to 20 weight%. (D) A substance having a metal ion capturing ability: 0.5 to 30% by weight.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The alkaline agent as the component (a) is preferably added in an amount of 0.5 to 30% by weight in the detergent composition.
More preferably, it is added in an amount of 0.5 to 20% by weight.
If the content is 0.5% by weight, the cleaning performance is deteriorated, while if it exceeds 20% by weight, the liquid property becomes unstable. (B)
As the component surfactant, a surfactant represented by the following general formula (1) is compounded.

[0015]

Embedded image R ₁ O (EO) m (PO) nR ₂ ... (1) (R ₁ : a linear or branched alkyl group, alkenyl group or alkyl group having 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms) Phenyl group R ₂ : hydrogen or a linear or branched alkyl group, alkenyl group or alkylphenyl group having 1 to 8 carbon atoms EO: additional unit of ethylene oxide PO: additional unit of propylene oxide m, n: 0 to 10 together M + n is an integer value of 1 or more, not 0, and random addition or block addition may be performed when EO or PO is added.
The order of adding O and PO does not matter. When the values of m and n exceed 10, the foaming during cleaning by the washing machine is severe and the operation of the washing machine is hindered. Preferably m = 2-10, n =
It is 0-5.

The surfactant as the component (b) is contained in the composition of the present invention in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight. If the blending amount is less than 0.1% by weight, the detergency against oil stains and the effect of preventing recontamination are insufficient.
On the other hand, if it exceeds 20% by weight, it is difficult to obtain a stable liquid property, and foaming is severe during cleaning by the washing machine, which causes an obstacle to the operation of the washing machine.

Examples of the liquidity improver of the component (c) include aromatic carboxylic acids such as benzoic acid and p-toluic acid or salts thereof; benzenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, m-xylenesulfone. Aromatic sulfonic acid such as acid or a salt thereof; alkyl sulfate ester salt such as 2-ethylhexyl sulfate ester salt, 2-ethylethoxyhexyl sulfate ester salt, polyoxyethylene monobutyl ether sulfate ester salt (average number of moles of ethylene oxide added is 1) Alternatively, polyoxyethylene alkyl ether sulfate ester salt is used, and more preferably m-xylene sulfonate salt and / or 2-ethylhexyl sulfate ester salt is used. As the salt, water-soluble salts such as alkali metal salts such as sodium and potassium, ammonium salts, organic amines such as monoethanolamine, diethanolamine and triethanolamine are used.

The liquidity improver as the component (c) is 0.5 to 20% by weight, preferably 0.5 to 20% by weight in the detergent composition of the present invention.
10 wt% is compounded. If the content is less than 0.5% by weight, the effect of improving the liquidity is insufficient and the stability as a solution is poor. On the other hand, if it exceeds 20% by weight, foaming is severe during cleaning by the cleaning machine and the operation of the cleaning machine is disturbed. Occurs.

In the present invention, by further incorporating a substance having a metal ion-capturing ability as the component (d), the finish (washing-up) of objects to be washed such as tableware and glasses can be further improved.

Examples of the component (d) having a metal ion-capturing ability include hydroxycarboxylic acids such as malic acid, citric acid, gluconic acid and heptonic acid or salts thereof; iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepenta. Aminocarboxylic acid such as acetic acid, triethylenetetraminehexaacetic acid, cyclohexane-1,2-diaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid or a salt thereof; polyacrylic acid or a salt thereof, represented by the following chemical formula (2) A water-soluble polymer substance such as a copolymer obtained from the represented monomer copolymerizable with maleic acid or maleic anhydride or a salt thereof is used.

[0021]

[Chemical 5] _{(R 1, R 2, R} 3, R 4: a hydrogen or an alkyl group having 1 to 5 carbon atoms, a phenyl group, an alkoxy group or a carboxyl group M: hydrogen, water-soluble salts, such as alkali metal or organic amine x / y ( Copolymerization molar ratio) = 1/10 to 10/1 weight average molecular weight: 1,000 to 100,000) As the salt in the component (d), alkali metal salts such as sodium and potassium, water-soluble organic amine salts and the like. Sodium salt is used.

Among the components (d), the above-mentioned general formula (2)
A homopolymer of maleic acid or maleic anhydride represented by the following, a copolymer obtained from a monomer copolymerizable therewith, or a water-soluble salt of these polymers is preferable.

The substance (d) having a metal ion-capturing ability is preferably incorporated in the detergent composition of the present invention in an amount of 0.5 to 30% by weight, more preferably 3.0 to 20% by weight. %. If the blending amount is less than 0.5% by weight, the effect of improving the finishability of the article to be washed is not sufficient, while 30% by weight
If it exceeds, the glass and tableware will be eroded, which may change the appearance of the object to be washed.

In the cleaning composition of the present invention, in addition to the above-mentioned essential components, optional components such as dyes, fragrances, enzymes, oxidizers, etc. can be blended, and 100 wt. By setting it as%, the final liquid hard surface cleaner composition can be obtained.

[0025]

According to the present invention, by combining (a) an alkaline agent, (b) a specific surfactant and (c) a specific liquidity improving agent to form a detergent composition, an oil composition can be obtained. It is possible to obtain a liquid hard surface cleaner composition having a good liquid property, which has excellent cleaning power against dirt and anti-soil redeposition effect. Further, according to the present invention, by further using a substance having a metal ion-capturing ability as the component (d), it is possible to further improve the finish of articles to be washed such as tableware and glasses.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples, but prior to this, the evaluation method adopted in the examples will be described.

(1) Washing performance and oil recontamination prevention effect As a washing machine, a one-door type dishwasher for professional use (JWD-6 type manufactured by Ishikawajima Harima Heavy Industries Ltd.) was used to remove oil stains (butter). Painted dish), protein stain (yolk-coated dish)
Under normal washing conditions (washing temperature; 60 ° C., washing concentration;
0.2%, cleaning time; 40 sec. , Rinsing temperature; 80
C., rinsing time; 15 sec. ), And after drying, the cleaning power is visually evaluated. In addition, when cleaning, put clean glass and tableware with no stain on it, and after drying, visually check the effect of preventing oil redeposition.

(I) Criteria for Detergency ⊚: Soil was completely removed. ◯: Most of the dirt was removed. Δ: Stain removal is sufficient. X: Soil is hardly removed. (Ii) Criteria for preventing oil recontamination effect ⊚: Dirt has not redeposited. ◯: Slightly adhered, but in a washed state. Δ: Soil redeposition occurs. X: Many redeposition of stains.

(2) Machine operability When the cleaning performance is evaluated in (1) above, the machine operability is simultaneously evaluated. Judgment criteria ◎: There is almost no foaming and there is no hindrance to the operation of the washing machine. ○: There is some foaming but there is no problem in the operation of the washing machine. Δ: There is foaming and there is some trouble in the operation of the washing machine. X: A lot of foaming occurs, which hinders the operation of the washing machine.

(3) Finishing property of crystal glass (finishing property) As in the test method of (1) above, using a commercial dishwasher (JWD-6 type manufactured by Ishikawajima Harima Heavy Industries Co., Ltd.) Cleaning conditions (cleaner concentration: 0.2%, cleaning temperature: 60
C., washing time; 40 sec. , Rinse temperature; 80 ° C., rinse time; 15 sec. ) Wash the porcelain and crystal glass with), and after drying, visually inspect the surface condition of the crystal glass. Judgment Criteria ◎: The finish is very good. ◯: Good finish. Δ: Some cloudiness is observed. X: White turbidity is severe.

(4) Liquidity 100 ml of the sample is placed in a 100 ml vinyl chloride container and stored under various storage conditions for 1 month to evaluate the liquidity. Judgment Criteria ○: Transparent liquid △: Fine liquid ×: Separation or solidification

Examples 1 to 11 Each liquid hard surface cleaner composition having the composition shown in Tables 2 and 4 was prepared, and the components (a), (b) and (c) were used as essential components in Example 1 For 5 to 5, the cleaning performance, oil recontamination prevention effect, machine operability and liquidity were evaluated, and (a),
Example 6 in which components (b), (c) and (d) are essential components
The finishability was further evaluated for Nos. 13 to 13. The results are shown in Tables 3 and 5. The structures of the component (b) and the optional component (nonionic surfactant outside the range of the component (b)) are shown in Table 1 below.

[0033]

[Table 1] Table 1: Structure of specific surfactant of component (b) R ₁ O (EO) m (PO) nR ₂ R ₁ Average number of added moles R ₂ m n Surfactant A C ₉ ~ ₁₁ alkyl group 5 0 methyl surfactant B C ₁₂ ~ ₁₄ alkyl group 7 4 hydrogen surfactant C C ₁₃ ~ ₁₅ alkyl group 5 2 methyl groups surfactant D C ₁₃ ~ ₁₅ alkyl group 0 4 ethyl surfactant E C ₁₈ alkyl groups 8 0 hexyl surfactant F C ₉ alkyl phenyl group 5 0 methyl surfactant G * ¹ C ₁₂ ~ ₁₄ alkyl group 12 0 hydrogen * 1) Surfactant G has an excessively large average number of moles of EO added, and is outside the range of the specific surfactant of component (b) of the present invention.

[0034]

[Table 2] Table 2: Composition of cleaning agents Example ratio Comparative composition (wt%) 1 2 3 4 5 1 2 3 4 (a) component Caustic potash 15 − 3 6 10 5 − 3 − Caustic soda − 5 3 3 − − 15 3 − (b) Component Surfactant A 0.7 1 − − − − − 3 − 7 Surfactant C − − 2 0.5 1 − − − − (c) Component m-XS-Na − − − − − 5 − − − − P-Toluic acid 3 − − − − − − − − AS-Na 2.5 3 5 6.5 1.2 − − − 5 Optional component Surfactant G − − − − − − − 5 − NTA-3Na potassium pyrophosphate − − − − − − − 7 − EDTA-4Na − − − − − − 10 − 4 Citric acid 3-Na − − 3 − − − − − − Ion-exchanged water balance surfactant A, C, G: As shown in Table 1 (however, the surfactant G is outside the range of the component (b) of the present invention m-XS-Na: sodium m-xylene sulfonate AS-Na: 2-ethylhexyl sulfuric acid ester sodium NTA-3Na : Nito Rotori Sodium EDTA-4Na: ethylenediaminetetraacetic acid sodium

[0035]

[Table 3] Table 3: Evaluation results of cleaning agents Example comparison Comparative evaluation results 1 2 3 4 5 1 2 3 4 4 Cleaning performance Oil stains ◎ ◎ ◎ ◎ ○ ◎ △ ◎ ◎ ◎ ○ Protein stains ○ ○ ○ ◎ ◎ ○ ◎ ○ × Recontamination prevention effect ◎ ◎ ◎ ○ ◎ × ◎ ◎ ◎ ◎ Machine operability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ × ◎ Liquidity 40 ℃ ○ ○ ○ ○ ○ ○ × × × Room temperature ○ ○ ○ ○ ○ ○ × × ○ 5 ℃ ○ ○ ○ ○ ○ ○ × × ○

[0036]

[Table 4]Table 4: Composition of detergent Example Comparative example Composition (wt%) 6 7 8 9 10 11 12 13 5 6 7 8 (a) Component Caustic potassium-5 15 6-0.6 3 3 20-5 0.3 Caustic soda 4.5---3---5 4.5 10-Potassium carbonate − − − 1 − − − − 3 − − − (b) Component Surfactant B − 1 − − − − − − − − − − Surfactant C 1.5 − − − 3 6 0.7 − 5 − − 5 Surfactant D − − 0.5 − − − − − − − − − Surfactant E − − − 0.5 − − − − − − − −Surfactant F − − − − − − − 1 − − − − (c) Component m-XS-Na − 1 − − − − − − − − 10 − AS-Na 3 2 2.5 8 8 8 7 2 − − − 10p-toluic acid − − 3 − − − − − − − − − (d) Component NTA-3Na 2 − − − − − − − − − − 0.4 Citric acid -3Na − 3 − 6 5 − − − − − − − PA-Na − − 10 − − − − − − − − − Copolymer 1 − 5 − − 7 3 − − − − 10 − −Copolymer 2 − − − − − − 45 5 − − − − Arbitrary components PG − − 1 − − − − − − − − 2 Ethanol − 2 − − 1 − 1 − − 3 2 1 Ion-exchanged water balance Surfactants B to F: As shown in Table 1 m-XS-Na: m-xylene sulfonic acid soda AS-Na: 2-ethylhexyl sulfuric acid ester soda NTA-3Na: nitrilotriacetic acid soda PA-Na: polyacrylic acid soda (weight Average molecular weight 1200) Copolymer 1: C5 olefin / sodium maleic anhydride copolymer (copolymerization ratio = 1/1, weight average molecular weight 6000) Copolymer 2: acrylic acid / sodium maleate copolymer (copolymerization ratio = 4 / 6. Weight average molecular weight 3000) PG: Propylene glycol

[0037]

[Table 5]Table 5: Evaluation results of cleaning agents Example Comparative example Evaluation results 6 7 8 9 10 11 12 13 5 6 7 8 Cleaning performance Oil stains ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ◎ △ △ ○Protein stain ○ ○ ◎ ◎ ○ ○ ○ ○ ◎ ○ ◎ △ Preventing recontamination ◎ ○ ◎ ○ ◎ ◎ ○ ◎ ◎ △ × ◎ Finishability ○ ◎ ○ ○ ◎ ◎ ○ ○ × ◎ ○ △ Machine operability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ○ Liquid 40 ℃ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ Room temperature ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ 5 ℃ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○

Claims (4)

[Claims] 1. (a) Alkaline agent: 0.5 to 30% by weight (b) Surfactant represented by the following general formula (1): 0.1 to 20% by weight; ₁ O (EO) m (PO) nR ₂ (1) (R ₁ : a linear or branched alkyl group, alkenyl group or alkylphenyl group having 6 to 24 carbon atoms R ₂ : hydrogen or 1 to 8 carbon atoms Linear or branched alkyl group, alkenyl group or alkylphenyl group EO: Addition unit of ethylene oxide PO: Addition unit of propylene oxide m, n: 0 to 10 and not both 0, m + n is an integer value of 1 or more, When EO and PO are added, random addition or block addition may be performed.
The order of adding O and PO does not matter. ) (C) One or more kinds of liquidity improvers selected from aromatic carboxylic acids, aromatic sulfonic acids and salts thereof, alkyl sulfate ester salts and polyoxyethylene alkyl ether sulfate ester salts: 0.5 to 20% by weight A liquid hard surface cleaner composition comprising: 2. The liquid hard surface cleaner composition according to claim 1, wherein the component (c) is a 2-ethylhexyl sulfate ester salt. 3. The liquid hard surface cleaning composition according to claim 1, further comprising 0.5 to 30% by weight of a substance having a metal ion-trapping ability as the component (d). 4. A copolymer obtained from a monomer capable of being copolymerized with maleic acid or maleic anhydride represented by the following general formula (2): The liquid hard surface cleaner composition according to claim 3, which is Embedded image _{(R 1, R 2, R} 3, R 4: a hydrogen or an alkyl group having 1 to 5 carbon atoms, a phenyl group, an alkoxy group or a carboxyl group M: hydrogen, water-soluble salts, such as alkali metal or organic amine x / y ( Copolymerization molar ratio) = 1/10 to 10/1 weight average molecular weight: 1,000 to 100,000)