JPH06136395A - Hard surface cleaning composition - Google Patents

Abstract

(57) [Summary] (Corrected) [Composition] Alkaline agent: 1-48%, HLB 1-12
Of 1 to 10% and a copolymer obtained from maleic acid represented by the formula (1) or maleic anhydride and another monomer copolymerizable therewith or a water-soluble salt thereof: 1 to 25% Hard surface cleaner composition. [Effect] Excellent cleaning power against oil stains can be obtained, and it is possible to reduce or eliminate prior hand washing. Prevents erosion of patterns such as gold patterns of tableware and lead erosion of crystal glass, and can prevent water-insoluble substances from adhering to and remaining on the washing machine or tableware in processes such as washing, rinsing and drying. . _{(R 1, R 2, R} 3, R 4: hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group or carboxyl group having 1 to 5 carbon atoms M: hydrogen, an alkali metal or alkanolamine n / m (copolymer (Mole ratio): 10/1 to 1/10 Weight average molecular weight: 1,000 to 100,000)

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition suitable for cleaning hard surfaces, particularly for cleaning using a cleaning machine.

[0002]

2. Description of the Related Art Due to a recent labor shortage, maintenance of working environment, thorough hygiene control, etc., the washing of a large amount of tableware and mechanical parts has become common due to mechanization and automation. In addition, water usage has increased due to changes in lifestyle, industrial development, etc., and the size of water storage has increased. Due to the large amount of water secured, it is being used to store topsoil and use it at high altitudes (several times).
The amount of polyvalent metal ions in the water used for washing using a washing machine is increasing with the resorting of hotels and restaurants at the beach. On the other hand, food menus have become diversified, and there is an increase in the adhesion of oily and protein stains on tableware and the like. In addition, tableware with gold patterns and high-end items such as crystal glasses are increasingly used. Under these circumstances, there is currently a demand for a cleaning agent that is suitable for use in a washing machine, has excellent cleaning power, and does not damage tableware.

Conventionally, a cleaning agent which has been used for cleaning without using a cleaning machine contains a large amount of anionic surfactant, cationic surfactant, zwitterionic surfactant, nonionic surfactant, or a mixture thereof. It is a cleaning agent that contains and is excellent in cleaning ability and foaming performance, but if it is applied to a washing machine that quickly treats a large amount of objects to be washed, a large amount of bubbles will be generated in the pump that supplies the cleaning liquid and the pump will operate. Suppress or stop. further,
When the cleaning liquid is sprayed on the object to be cleaned, the cleaning ability may not be exhibited due to a large amount of bubbles. At the same time, rinsing requires a large amount of water and time, which is not economical.

On the other hand, the followings have been reported as the cleaning agents used for cleaning using a cleaning machine. (1) Detergent containing caustic alkali and water-soluble glycol ether (JP-A-61-296097) and detergent containing caustic alkali and water-soluble alkanolamine (JP-A-61-296098): for oily stains The main point is cleaning and removal.

(2) Liquid detergent containing tripolyphosphate, silicate, caustic potash, alkali hypochlorite and water (JP-A-62-50399), caustic alkali, sodium tripolyphosphate and silicate , A detergent containing a polymer substance (Japanese Patent Laid-Open No. 63-37838), which mainly focuses on the chelating ability and the washing ability of polyvalent metal ions.

(3) Detergent composition comprising caustic alkali and 2-hydroxyethyliminodiacetic acid salt (Japanese Patent Publication No. 2-27397) and detergent composition comprising caustic alkali and alkali metal salt of nitrilotriacetic acid (Japanese Patent Publication No. 3-60358): Mainly the chelating ability and cleaning ability of polyvalent metal ions.

(4) Cleaner composition for automatic dishwashing machine comprising caustic alkali, polyacrylic acid salt and specific water (JP-A-4-15299): Focusing on cleaning ability and sequestering ability of metal ions ing.

(5) A detergent composition for an automatic dishwashing machine, which comprises a nonionic surfactant, a calcium-supplementing chelating agent and an enzyme (JP-A-4-65494 and JP-A-4-65494).
No. 72397, Japanese Patent Application Laid-Open No. 4-72398): Focuses on the cleaning ability and the calcium supplementing chelating ability.

However, these techniques do not satisfy the following social demands as a detergent for hard surfaces using a washing machine. (1) Contaminated dishes can be easily washed with a washing machine, and oily stains can be highly washed and removed. (2) Prevent deterioration of high-end products such as tableware with gold patterns and glasses such as crystals. (3) Even if the water quality changes, a large cleaning ability can be obtained, and generation of scale adhering to the cleaning machine can be suppressed.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a hard surface cleaner composition which has excellent cleaning power against oil stains and is suitable for a cleaning machine. The present invention also provides a hard surface cleaning composition that prevents erosion and deterioration of tableware and does not adhere to water-insoluble substances on a washing machine or tableware.

[0011]

The hard surface cleaning composition of the present invention is characterized by containing the following components (a) and (b), or further component (c). (A) Alkaline agent. (B) A surfactant having an HLB of 1 to 12. (C) A copolymer obtained from maleic acid or maleic anhydride represented by Chemical formula 3 and another monomer copolymerizable therewith, or a water-soluble salt thereof.

[0012]

[Chemical 3] (R ₁ , R ₂ , R ₃ , R ₄ : hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group M: hydrogen, an alkali metal or an alkanolamine n / m (copolymerization (Mole ratio): 10/1 to 1/10 Weight average molecular weight: 1,000 to 100,000)

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the alkaline agent as the component (a),
Caustic alkali metal salts such as caustic sodium and caustic are preferably used, and sodium carbonate, potassium carbonate, sodium silicate, potassium silicate and the like can also be used. The alkaline agent as the component (a) is contained in the detergent composition in an amount of 1 to 48.
It is preferable to blend the composition in a weight percentage, and more preferably 3
-40% by weight.

As the component (b) surfactant, HLB is used.
Of 1 to 12, preferably HLB = 2 to 10 are used. Specific examples of the surfactant having such an HLB value include the nonionic surfactants represented by Chemical Formula 4 below.

[0015]

Embedded image R ₁ O (R ₂ O) nH (R ₁ : C 8-24, preferably 8-18 alkyl, alkenyl, alkylphenyl or alkenylphenyl R ₂ : C 2-3 Alkylene group n: represents the average number of moles of alkylene oxide added,
The alkylene oxide having 2 or 3 carbon atoms may be added alone or as a mixed addition. In the case of mixed addition, random addition or block addition may be used. )

The surfactant as the component (b) is preferably blended in the detergent composition in an amount of 1 to 10% by weight.

The polymer as the component (c) is represented by the following chemical formula 5.
A maleic acid or a copolymer of maleic anhydride with another monomer copolymerizable with or a water-soluble salt thereof is preferably used.

[0018]

[Chemical 5] _{(R 1, R 2, R} 3, R 4: hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group or a carboxyl group or a salt thereof of 1 to 5 carbon atoms M: hydrogen, an alkali metal or alkanolamine n / m (Copolymerization molar ratio): 10/1 to 1/10, preferably 10/2 to 2/10 weight average molecular weight: 1,000 to 100,000)

The polymer as the component (c) is preferably incorporated in the detergent composition in an amount of 1 to 25% by weight, more preferably 2 to 20% by weight.

The detergent composition of the present invention may further contain conventional optional components, for example, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, potassium silicate, sodium ethylenediaminetetraacetate, potassium nitrilotriacetic acid. A chelate builder such as the above, an organic acid such as citric acid or malic acid, sodium sulfate or the like can be added. The dosage form of the detergent composition of the present invention is not particularly limited, and may be, for example, liquid, powder or solid, or the like.

[0021]

EFFECTS OF THE INVENTION According to the present invention, by using (a) an alkaline agent and (b) a surfactant of HLB 1 to 10 in combination, a hard surface cleaning composition is obtained, which is excellent against oil stains. Detergency can be obtained. Recently, a wide range of traditional Japanese dishes, Chinese dishes, Western dishes, and other dishes have been added, leading to an increase in oil stains and protein stains, making it difficult to wash with a washing machine. Handwashing is often required before loading into the machine. According to the cleaning agent of the present invention, due to its excellent cleaning performance, it is possible to deal with the above-mentioned changes in the quality and amount of stains, and it is possible to reduce or eliminate hand washing in advance.

Further, according to the present invention, by additionally using a specific polymer as the component (c), it is possible to prevent erosion of tableware and adhesion of water-insoluble matter, and the following effects can be obtained. (1) It is possible to prevent erosion of patterns such as gold patterns of tableware and lead erosion of crystal glass. (2) Water-insoluble substances generated from polyvalent metal ions contained in used water and cleaning components or carbon dioxide gas in the air adhere to the washing machine or tableware during the steps such as washing, rinsing and drying. It can be suppressed from remaining.

[0023]

EXAMPLES Examples will be shown below, but prior to that, evaluation methods adopted in the examples will be shown. (1) Dirt removal ability and machine operability Using a one-door type dishwasher for professional use as a washing machine,
The usual cleaning conditions are a cleaning temperature of 60 ° C. and a cleaning agent concentration of 0.
The cleaning was performed for 1 minute of cleaning time under the condition of 2% and for 1 minute of rinsing time with hot water at 70 ° C.

The ability to remove protein stains was evaluated visually by the following criteria after washing using a dish coated with egg yolk. ◯: Almost all stains were removed ×: Insufficient removal of stains

The ability to remove oil stains was evaluated in the same manner as above using a buttered dish (melamine dish). ◯: Almost all stains were removed ×: Soil was removed, but recontamination was observed

The operability of the machine is as follows. ○: The machine operated properly ×: There was a lot of foaming and the machine did not operate properly

(2) Oil emulsifying and dispersing ability 100 g of a 0.2% washing liquid was added with 0.1 g of butter and shaken, and after 5 minutes, the state of emulsified and dispersed was visually judged. ◯: Emulsified and dispersed ×: Not emulsified and dispersed

(3) Change of gold porcelain and crystal glass A washing solution having the same concentration (0.2%) as that of the washing step of the washing machine was prepared using normal water admitted water (CaO: 50 ppm). After immersing the crystal glass for 1 week, the surface condition was observed. ◯: Coloring does not decrease (golden porcelain) White turbidity does not occur (crystal glass) X: Coloring decreases (golden porcelain) slightly opaque (crystal glass)

(4) Deposition of water-insoluble salt Adhesion Detergent was dissolved in the same rinse concentration (0.01-0.001%) as the rinse step of the washing machine using tap water (CaO: 50 ppm). To prepare a rinse solution,
The amount of water-insoluble substance produced and deposited was measured by the beaker test method in which water was evaporated to dryness at a high temperature of 0 ° C. ∘: Almost no water-insoluble matter adheres x: Many water-insoluble matter forms and adheres

Examples 1 to 4 Each detergent composition having the composition shown in Table 1 was prepared, and protein stain removing ability, oil stain removing ability, machine operability, and oil emulsifying and dispersing ability were evaluated. The results are shown in Table 1.

[0031]

TABLE 1: Evaluation comparisons example the composition of detergents implementation Example 1 2 3 4 1 2 3 4 detergent composition (wt%): caustic Na 40 30 - - 48 20 - - caustic K - - 20 10 − − 10 1 Tripolyphosphate Na 30 − − − 20 − − − Pyrophosphate K − − − 5 − − 10 − EDTA-4Na − 20 − − − − − − NTA-3K − − 10 − − − − − Carbonic acid Na − − − − − 20 − − Orthosilicate K − − − − − − − − 5 Surfactant Z 1 − − − − − − − Surfactant Y − 5 − − − − − − Surfactant A − − 0.1 15 1 − − − Surfactant B − − − − − 2 − − Surfactant C − − − − − − 5 − Surfactant D − − − − − − − 10 Sulfuric acid Na 29 45 − − 31 58 − − Water − − 69.9 70 − − 75 84 Evaluation: Protein stain removal ability ○ ○ ○ ○ ○ ○ ○ ○ Oil stain removal ability × × × × ○ ○ ○ ○ Machine operation Motility × × ○ × ○ ○ ○ ○ Oil emulsifying and dispersing ability ○ ○ × ○ ○ ○ ○ ○ Note) Surfactant Z: Polyoxyethylene (P = 20) Stearyl ether “HLB = 13” Surfactant Y: Poly Oxypropylene (P = 30) Lauryl ether “HLB = 18” Surfactant A: Polyoxyethylene (P = 7) Stearyl ether “HLB = 8” Surfactant B: Polyoxypropylene (P = 3) Lauryl ether “ HLB = 1 "surfactant C: polyoxyethylene (P = 7) · polyoxypropylene _{(P = 2) C 6 ~C} 10 alkyl ether" HLB = 3 "surfactant D: polyoxyethylene (P = 10 ) Stearyl ether "HLB = 10" and polyoxypropylene (P = 2) 1: 1 mixture of lauryl ether "HLB = 1" EDTA-4Na: ethylene Diamine tetraacetic acid tetrasodium NTA-3K: Nitrilotriacetic acid trisodium

As shown in Comparative Examples 1 and 2 in Table 1, sodium hydroxide or caustic potassium as a strong alkaline agent and high HL were used.
The conventional detergent composed of the surfactant of B and sodium tripolyphosphate or tetrasodium ethylenediaminetetraacetate has the ability to remove protein stains, but oily stains remain on the dishes and are not sufficiently removed. . On the other hand, Example 1
The detergents of the present invention using the surfactants of HLB = 1 to 10 shown in FIGS. 4 to 4 achieve the removal of oil and are emulsified and dispersed to eliminate the residue on the dishes, and the washing machine also operates normally. ing.

As shown in Comparative Examples 3 and 4, HL
Even if the surfactant of B = 1 to 10 is used, if the compounding amount is too small, the cleaning ability is insufficient, while if it is too large, the machine operability and the oil stain removing ability are deteriorated due to foaming.

Examples 5 to 10 A cleaning agent having the composition shown in Table 2 was prepared, and gold porcelain was changed.
The change in crystal glass, the degree of water-insoluble salt formation, the oil emulsifying and dispersing ability, the oil stain removing ability, and the machine operability were evaluated, and the results are shown in Table 2.

[0035]

[Table 2]Table 2: Composition of cleaning agent and its evaluation Comparative example Example 5 6 7 8 5 6 7 8 9 10 Detergent composition (wt%): Caustic Na 45 30-4.5 30 20-4.5 3 2 Caustic K--15 ---- 10 ----- EDTA-4Na 20-10 ---------- NTA-3K-15 −5 −−−−−− Specific molecule A −−−−− 10 −−−−− Specific molecule B −−−−−- 8 −−−− Specific molecule C −−−−−− 6 −−− Specific molecule D − − − − − − − 4 − − Surfactant A − − − − − − − 12 − Surfactant B − − − − − − − − − 3 Surfactant C − − − − 4 − − − − − Surfactant D − − − − − 3 − − − − Surfactant E − − − − − − 2 − − − Sulfuric acid Na 35 55 − − 56 69 − − − − Water − − 75 90.5 − − 82 91.5 93 94 Evaluation: Change in gold porcelain × × × × ○ ○ ○ ○ ○ ○ Crystal glass × × × × ○ ○ ○ ○ ○ ○ Change in water-insoluble matter formation × × × × ○ ○ ○ ○ ○ ○ Oil emulsification dispersion ability × × × × ○ ○ ○ ○ ○ ○ Oil stain removal capacity × × × × ○ ○ ○ ○ ○ ○ Machine operability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Note) Surfactant A: Polyoxyethylene (P = 7) Stearyl ether “HLB = 8” Surfactant B: Polyoxypropylene (P = 3) Lauryl ether “HLB = 1” Surfactant C: Polyoxyethylene (P = 7) · Polio
Xypropylene (P = 2) C₆~ C_TenAlkyl ether
"HLB = 3" Surfactant D: Polyoxyethylene (P = 10) Stearyl ether "HLB = 10" and polyoxypro
Pyrene (P = 2) 1: 1 mixture of lauryl ether “HLB = 1” Surfactant E: polyoxyethylene (P = 7) / polio
Xypropylene (P = 3) C_Ten~ C₁₆Alkyl ether
“HLB = 7” Specific molecules A to D: Chemical formula 6 below, the contents of which are as shown in Table 3

[0036]

[Chemical 6]

[0037]

TABLE 3: Structure, properties specific high content child of the specific polymer A B C D E F M Na Na Na Na K K R 1 CH 3 H H COONa H H R 2 CH 3 H H CH 3 H HR ₃ CH ₃ H CH ₃ CH ₃ H HR ₄ CH ₃ C ₃ H ₇ C ₂ H ₅ C ₂ H ₅ COOK OCH ₃ n / m (molar ratio) 6/4 8/2 5/5 1/9 9/1 7/3 Weight average molecular weight 10,000 100,000 20,000 5,000 20,000 20,000

As shown in Table 2, the aminocarboxylic acid type chelating agents such as 3-sodium nitrilotriacetic acid and 4-potassium ethylenediaminetetraacetic acid are more likely to interact with polyvalent metal ions as the number of carbonyl groups held in the molecule increases. It is known to form a stable complex, but in the presence of an alkaline agent, each metal of tableware with a pattern such as a gold pattern on ceramics and porcelain, crystal glass containing lead, etc. is eluted and damaged. Let Further, a large amount of water-insoluble matter is produced, and this water-insoluble matter adheres to a washing machine or tableware and becomes a scale.

On the other hand, in the examples shown in Table 2, the results of observing the surface condition of the article to be washed and evaluating the amount of water-insoluble matter produced by blending a specific polymer substance in the same manner as described above The surface condition of the object shows almost no change. In addition, the formation of water-insoluble matter was hardly observed, and the scale did not adhere. Further, the emulsifying and dispersing ability and the removal of oil are achieved, and the washing machine operates normally.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshimi Kaji 1-3-7 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (5)

[Claims] 1. A hard surface cleaner composition comprising (a) an alkaline agent: 1 to 48% by weight and (b) a surfactant having an HLB of 1 to 12: 1 to 10% by weight. 2. From (a) an alkaline agent, (b) a surfactant having an HLB of 1 to 12, and (c) a maleic acid represented by Chemical formula 1 or another monomer copolymerizable with maleic anhydride. A hard surface cleaner composition comprising the resulting copolymer or a water-soluble salt thereof. [Chemical 1] (R ₁ , R ₂ , R ₃ , R ₄ : hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group M: hydrogen, an alkali metal or an alkanolamine n / m (copolymerization (Mole ratio): 10/1 to 1/10 Weight average molecular weight: 1,000 to 100,000) 3. The component (a) is contained in an amount of 1 to 48% by weight,
The hard surface cleaning composition according to claim 2, which contains 1 to 10% by weight of the component (b) and 1 to 25% by weight of the component (c). 4. The hard surface cleaning composition according to claim 1, wherein the component (a) is a caustic alkali metal salt. 5. The nonionic surfactant represented by the chemical formula 2 wherein the HLB is 1 to 10 as the component (b).
4. The hard surface cleaning composition according to any one of 4 above. Embedded image R ₁ O (R ₂ O) nH (R ₁ : an alkyl group having 8 to 24 carbon atoms, an alkenyl group,
Alkyl phenyl group or alkenyl phenyl group R ₂ : an alkylene group having 2 to 3 carbon atoms, n: an average number of moles of added alkylene oxide,
The alkylene oxide having 2 or 3 carbon atoms may be added alone or as a mixed addition. In the case of mixed addition, random addition or block addition may be used. )