JP2012087170A - Powder detergent composition for professional dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition for professional automatic dishwashers having excellent detergency towards protein smears and free from problems on storage and dangerousness in handling.SOLUTION: The powder detergent composition for professional automatic dishwashers contains 10-18 mass% (expressed in terms of anhydride) of (A) sodium metasilicate, 10-35 mass% of (B) a sodium salt of a maleic acid/acrylic acid copolymer, 5-35 mass% (expressed in terms of anhydride) of (C) sodium citrate and/or potassium citrate, and 25-60 mass% of (D) potassium chloride, wherein the total amount of the components (B) and (C) is 25-50 mass%.

Description

  The present invention relates to a powder detergent composition for commercial dishwashers.

Unlike household dishwasher detergent compositions, it is necessary to perform washing at high temperatures and in a short time, and in order to exert cleaning power such as protein stains, Strong alkalis such as sodium hydroxide and potassium hydroxide are used (for example, see Patent Documents 1 and 2).
However, since these strong alkalis are deleterious substances, in addition to storage problems, there are problems in handling such as danger in work and the need for neutralization in the post-treatment of the waste liquid.

JP-A-6-136395 JP 2007-131659 A

  Therefore, an object of the present invention is to provide a cleaning composition for a commercial automatic dishwashing machine that has excellent protein soil cleaning power and does not have storage problems or handling risks.

According to the present invention, (A) 10% by mass or more of sodium metasilicate in anhydrous conversion,
(B) 10% by mass or more of sodium salt of maleic acid / acrylic acid copolymer,
(C) 5% by mass or more of sodium citrate and / or potassium citrate in anhydrous conversion,
as well as
(D) contains 25-60 mass% potassium chloride,
And the sum total of (B) and (C) component is 25 mass% or more,
A powder detergent composition for commercial automatic dishwashers is provided.

  The cleaning composition for commercial automatic dishwashers of the present invention is not only excellent in protein stain cleaning power, but also contains no strong alkali, so there is no storage problem or handling risk. The composition of the present invention is also excellent in scale (dullness) removal ability and prevention ability. The composition of the present invention is also excellent in storage stability.

[Component A] Sodium Metasilicate Sodium metasilicate generally has moderate alkalinity and can denature proteins. In the present invention, sodium metasilicate plays a role of improving detergency against protein stains due to its alkalinity. Sodium metasilicate is also excellent in powder physical properties.
Examples of sodium metasilicate include anhydrous pentahydrate and 9 hydrate, and any of them can be used in the present invention, but anhydrous sodium metasilicate is more preferable. For example, it is marketed by Yakusei Kasei under the trade name “anhydrous metasilicate soda”.
Note that with general-purpose alkaline components such as sodium carbonate and potassium carbonate, the scale adheres to the object to be cleaned after cleaning. With orthosilicate sodium, it is difficult to obtain a composition with good powder properties. Nos. 1 to 3 sodium silicate is a liquid and cannot be used in terms of powder properties.
In the composition of the present invention, the content of the component A is 10% by mass or more, and preferably 18% by mass or less. More preferably, it is 12 mass% or more and 14 mass% or less. If it is less than 10% by mass, the protein soil cleaning power is inferior due to lack of alkaline tea. If it exceeds 18% by mass, it is not preferable in that the powder physical properties deteriorate, for example, caking occurs during storage.

[Component B] Sodium salt of acrylic acid / maleic acid copolymer In the present invention, component B prevents Ca and Mg ions present in the cleaning solution from binding to carbonate ions and adhering to hard surfaces such as tableware. In addition to the ability to remove these ions, it also has the effect of weakening the force of protein stains adhering to the hard surface, improving the protein stain cleaning power.
It is preferable that the weight average molecular weight of B component is 2000-100,000. Within such a range, the ability to remove ions is excellent. In addition, the weight average molecular weight of B component can be measured by the gel permeation chromatography which made the standard substance sodium polyacrylate.
The copolymerization ratio (molar ratio) of acrylic acid / maleene is preferably 75/25 to 50/50.
The component B can be synthesized or commercially available. Specific examples of commercially available products include AQUALIC TL400 (acrylic acid / maleic acid copolymer sodium salt, molecular weight: 50000) manufactured by Nippon Shokubai Co., Ltd., Socaran CP7 and / or CP5 (both acrylic acid manufactured by BASF). / Maleic acid copolymer sodium salt CP7 molecular weight: 50000, CP5 molecular weight: 70000). Also, a product obtained by neutralizing socalan CP12S (acrylic acid / maleic acid copolymer molecular weight: 3000) manufactured by BASF with sodium hydroxide and evaporating to dryness with an evaporator can be used.
In addition, polyacrylic acid or a salt thereof has a slight scale preventing ability, but does not have a removing ability. Moreover, it does not have the effect | action which weakens the force which protein dirt adheres to the hard surface.
In the composition of the present invention, the content of the component B is 10% by mass or more, and preferably 35% by mass or less. More preferably, it is 12 mass% or more and 20 mass% or less. If it is less than 10% by mass, the protein soil detergency is reduced. Scaling prevention and descaling capabilities are also lacking. When it exceeds 35 mass%, it is not preferable at the point that storage stability falls.

[C component] Sodium citrate and / or potassium citrate In the present invention, the C component co-operates with the B component, and Ca and Mg ions present in the cleaning liquid bind to carbonate ions and adhere to the hard surface. In addition to preventing this, it has an action of weakening the force of protein dirt adhering to the hard surface, so that the protein dirt detergency can be improved. In the present invention, the terms “sodium citrate” and “potassium citrate” include hydrates.
As the component C, it is preferable that all three carboxyl groups in the molecule form a sodium salt or a potassium salt. In the case of trisodium salt, dihydrate is preferable from the viewpoint of stability. In the case of tripotassium salt, monohydrate is preferable from the viewpoint of stability.
Trisodium citrate dihydrate is commercially available from, for example, Fuso Chemical Industries, and tripotassium citrate monohydrate is commercially available from, for example, Kanto Chemical.
Note that potassium carbonate is not preferable because it causes scale generation. The ethylenediaminetetraacetic acid (EDTA) salt does not work synergistically with the component B, and cannot improve the protein soil cleaning power.
In the composition of the present invention, the content of component C is 5% by mass or more and preferably 35% by mass or less. More preferably, it is 10 mass% or more and 30 mass% or less. If it is less than 5% by mass, the protein soil detergency is insufficient. The ability to prevent scale is also reduced. When it exceeds 35 mass%, it is not preferable at the point which the storage stability of a composition falls.

[D component] Potassium chloride In the present invention, when D component coexists with B component and C component, it exerts a “booster effect” that further enhances the action of weakening the force of protein stains adhering to the hard surface. can do. This is particularly effective when the total amount of B + C is small.
Note that potassium carbonate is not preferable because it causes scale generation.
In the composition of the present invention, the content of component D is 25% by mass or more, and preferably 60% by mass or less. More preferably, it is 30 mass% or more and 50 mass% or less. If it is less than 25% by mass, the protein soil detergency is insufficient. If it exceeds 35% by mass, it is not preferable in that the powder smoothness is lowered.

[(B + C) total mass%]
In the composition of the present invention, the total amount of B and C is 25% by mass or more, and preferably 50% by mass or less. More preferably, it is 30 mass% or more and 40 mass% or less. If it is less than 25% by mass, the protein soil detergency is insufficient. When it exceeds 50 mass%, it is not preferable at the point that storage stability deteriorates.

[E component] Nonionic surfactant The composition of this invention can contain the nonionic surfactant further represented by following formula (1). By adding a nonionic surfactant represented by the following formula (1), it is possible to exhibit further excellent oil stain cleaning power.
R ¹ —O— (EO) _p (PO) _q H (1)
In the formula, R ¹ is a linear or branched hydrocarbon group having 8 to 20 carbon atoms, and preferably R ¹ is a linear or branched hydrocarbon having 12 to 13 carbon atoms. A linear or branched alkyl group having 8 to 20 carbon atoms is preferred. More preferred is a branched alkyl group having 8 to 20 carbon atoms.
EO represents an ethylene oxide group, and PO represents a propylene oxide group.
p and q each independently represents a number of 1 to 6. The number is preferably 2 to 4. If p exceeds 6, foaming is high and there is a risk of placing a burden on the automatic dishwasher. Moreover, when q exceeds 6, it is somewhat inferior in terms of the effect of cleaning oil stains. The total of p and q is preferably 3 or more and 10 or less. If the sum of p and q is less than 3, it is slightly inferior in terms of oil stain cleaning effect, and if it exceeds 10, foaming is increased.

The nonionic surfactant represented by the above formula (1) can be produced by a known method. For example, the raw material alcohol can be produced by adding EO and PO to alcohol having 12 to 13 carbon atoms and 20% branching rate, alcohol having 13 carbon atoms and 50% branching rate, and 2-ethylhexanol. .
Here, the “branch ratio” will be described by taking, as an example, a primary higher alcohol that is a raw material of the component represented by the formula (1). The higher alcohol is, for example, a mixture of a branched higher alcohol represented by the following formulas (2) to (3) and a linear higher alcohol represented by the formula (4).

In the formulas (2) to (4), R ²¹ , R ²³ and R ³¹ are alkyl groups having 1 or more carbon atoms, R ²² and R ³² are alkyl having 2 or more carbon atoms, and p is 1. , Q is 2 or 3, and r is an integer of 1 or more. The total number of carbon atoms in each formula is equal to the carbon number of R ¹ in formula (1).
“Branching rate” is the branched alkyl group in the compound represented by the above formula (2) + (3) with respect to the total mass of the alkyl moiety in the compound represented by the above formula (2) + (3) + (4). The ratio of the mass of

The branching rate can be measured under the following conditions using GC / MS.
<Measurement conditions for GC / MS>
Column: Ultra Alloy PY-1
Temperature: Oven; Temperature rising rate 10 ° C / min 50 → 310 ° C
Inlet; 310 ° C
Detector: 310 ° C
Carrier gas: He

  In the composition of the present invention, the content of the E component is preferably 1% by mass or more and 3% by mass or less. More preferably, it is 1 mass% or more and 2.5 mass% or less. If it is less than 1% by mass, the oil detergency is insufficient. When it exceeds 3 mass%, foaming is too high.

[Optional ingredients]
The composition of the present invention may further contain components usually used in a detergent composition for commercial dishwashers. Examples of such ingredients include solvents such as ethanol and purified water, plant extracts, antibacterial / bactericidal agents, deodorants, stabilizers, ionic surfactants, polymers, fragrances, and automatic dishwashers. Examples of the substances generally contained in cleaning agents for cleaning.

<Use form of composition>
The composition of the present invention is preferably used by dissolving in tap water immediately before use so that the composition concentration is about 0.15% by mass.

The compositions of the examples and comparative examples were prepared using the following ingredients.
[Component A]
Anhydrous sodium metasilicate Sodium orthosilicate (for comparison)
Potassium carbonate (for comparison)
[B component]
Maleic acid / acrylic acid copolymer sodium salt: manufactured by BASF, Sokalan CP7 (weight average molecular weight: 50000)
Polyacrylic acid (for comparison): BASF, Sokalan PA40 Powder (weight average molecular weight: 15,000)
[C component]
Tripotassium citrate monohydrate Trisodium citrate dihydrate [component D]
Potassium chloride Potassium carbonate (for comparison)
[E component]
Nonionic surfactant 1: C _n H _{2n + 1} O (EO) ₃ (PO) ₃ H (n = 12/13 mixture (mass ratio 65/35), manufactured by Shell under the trade name Neodol alcohol (branching rate 20%)) Average EO3PO3 mole adduct)
Nonionic surfactant 2: C _n H _{2n + 1} O (EO) ₃ (PO) ₄ H (n = 12/13 mixture (mass ratio 65/35), manufactured by Shell under the trade name Neodol alcohol (branching rate 20%)) Average EO3PO4 mole adduct)
Nonionic surfactant _{3: C n H 2n + 1} O (EO) 3 (PO) 3 H (n = 13, Sasol trade name Safol average EO3PO3 mole adduct of an alcohol (branch 50%))
Nonionic surfactant 4: CH ₃ (CH ₂ ) ₃ CH (CH ₂ CH ₃ ) CH ₂ O (EO) ₅ (PO) ₂ H (average EO5PO2 molar adduct of 2-ethylhexanol)

(Manufacture of nonionic surfactant 1)
As solution a, 47.69 g of aluminum nitrate nonahydrate and 24.43 g of manganese nitrate hexahydrate were dissolved in 68.03 g of magnesium nitrate hexahydrate with 450 g of deionized water. As solution b, 13.47 g of sodium carbonate was dissolved in 450 g of deionized water.
Solution a and solution b were added dropwise to a catalyst preparation tank in which 1800 g of deionized water had been previously charged, with an aqueous NaOH solution at pH = 9 and a temperature of 45 ° C. in 45 minutes. After aging for 1 hour, the mother liquor was filtered off, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain 30 g of a composite metal hydroxide.
This was calcined at 800 ° C. in a nitrogen atmosphere to obtain 19 g of a composite metal oxide catalyst mainly composed of magnesium oxide.
Next, 120 g of Neodol 23 (C12,13, branching rate 20%: manufactured by Shell) and 0.3 g of the above-mentioned catalyst were charged in the autoclave as raw alcohol, and the inside of the autoclave was replaced with nitrogen, followed by ascending with stirring. Warm up. Subsequently, 82 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180 ° C. and the pressure at 0.5 MPa or less. The obtained polyoxyalkylene ether had an average ethylene oxide addition mole number of 3.
Furthermore, 108 g of propylene oxide was introduced and reacted while maintaining the temperature of the autoclave at 180 ° C. and the pressure at 0.5 MPa or less. The average polypropylene oxide addition mole number of the obtained polyoxyalkylene ether was 3. After cooling the reaction solution to 80 ° C., 11 g of water and 3 g of Hyflo Supercell (Celite) as a filter aid are added, stirred and mixed, and then the catalyst is filtered through a cellulose filter (quantitative filter paper 5C: Advantech). Separated. In this way, a nonionic surfactant 1 was obtained.

(Production of nonionic surfactant 2)
Nonionic surfactant 2 was obtained in the same manner as Nonionic surfactant 1 except that 108 g of Neodol 23, 73 g of ethylene oxide, and 129 g of propylene oxide were used as raw materials.

(Production of nonionic surfactant 3)
A nonionic surfactant 3 was obtained in the same manner as the nonionic surfactant 1 except that Safol 23 (C12, 13, 50% branched: manufactured by Sasol Corporation) was used as the raw material alcohol.

(Production of nonionic surfactant 4)
The nonionic interface was the same as Nonionic Surfactant 1 except that 87 g of 2-ethylhexanol (manufactured by Diachemical Co.), 146 g of ethylene oxide, 77 g of propylene oxide, and 0.6 g of the reaction catalyst were used as the raw material alcohol. Activator 4 was obtained.

[Common ingredients]
Silicic anhydride: Tokuyama NP manufactured by Tokuyama Corporation

<Method for producing composition>
The above components A, B, C and D were put into a ribbon mixer, and while stirring at 25 rpm, the component E was sprayed at a pressure of 0.4 MPa using a nozzle JPX020 manufactured by Ikeuchi Co., Ltd. Next, 1.5% by mass of anhydrous silicic acid was added to the resulting mixture, balanced with sodium sulfate, and mixed at 25 rpm for 10 minutes to obtain a powder detergent composition for commercial automatic dishwashers.

[Evaluation of powder detergent composition for commercial automatic dishwashers]
The following evaluation tests were conducted using the powder detergent compositions for commercial automatic dishwashers of the Examples and Comparative Examples produced above. The results are shown in Tables 1-6.
<Evaluation of protein stain cleaning power>
5 g of commercially available cream cheese (Philadelphia cream cheese manufactured by Kraft Co., Ltd.) was spread thinly on a circular glass plate having a diameter of 21 cm, and then heated in a microwave to denature the protein. Four glass plates prepared in this way were set in a washing machine (manufactured by Hoshizaki, JWE-680A). Detergent concentration: 0.15% by mass, washing time: 2 minutes (temperature: 60 ° C.), rinsing time: 20 Washed in seconds (temperature: 80 ° C.). The amount of protein stains on the glass plate after washing was evaluated visually according to the following criteria, using the glass plate as a control when washed with only water without using the detergent composition.
Evaluation Criteria A: The protein soil removing ability was very excellent as compared with washing with water alone.
○: The protein soil removing ability was superior compared to washing with water alone.
(Triangle | delta): The protein dirt removal power was a grade which a little exceeded compared with the washing | cleaning only with water.
X: The protein soil removing ability was almost equal as compared with washing with water alone.

<Scale prevention ability evaluation>
75 ml of a detergent aqueous solution obtained by diluting the detergent compositions of Examples and Comparative Examples to 0.15% by mass with tap water (Edogawa-ku, Tokyo) having an American hardness of 90 ppm was added to a 100 ml capacity stainless beaker. Next, a stainless steel plate (SUS304, thickness x width x length = 1.0 x 25 x 75 mm) was put into this beaker, heated in a water bath, and when the liquid volume became 20-30 ml while evaporating the solution, The remaining aqueous solution of the cleaning solution was discarded. Next, about 100 ml of ion-exchanged water was placed in a stainless steel beaker and heated at 100 ° C. for 10 minutes, thereby rinsing the stainless steel plate.
Thereafter, the stainless steel plate was taken out from the beaker, and the amount of scale attached to the plate was visually determined according to the following criteria.
◎: Scale is not attached at all ○: Scale is mostly not attached △: Scale is partially attached ×: Scale is attached entirely

<Scale removal ability>
Place one clean glass cup (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) in the center of the automatic dishwasher (Matsushita Electric Industrial Co., Ltd., model NP-40SX2). 2 g was put into the machine and operated on a standard course (whole process of washing to rinsing) using hard water having a German hardness of 30 degrees. The cup obtained by this operation and covered with a white scale on the entire surface was washed with an aqueous detergent composition solution diluted to 0.15% by mass with tap water (Edogawa-ku, Tokyo) with an American hardness of 90 ppm. The finish was visually determined based on the following evaluation criteria.
Evaluation criteria:
A: No whitened material remains and no discomfort such as roughness is felt.
○: Some whitening residue is slightly observed.
Δ: A slight amount of whitened product was visually observed, and the overall transparency was lost.
X: The whitened material has not fallen.

<Evaluation of oil detergency>
35g of salad oil (Nisshin Salad Oil, manufactured by Nisshin Oillio Group Co., Ltd.) and a polypropylene lunch box coated with 35g of Carrero (inside dimensions: 113mm long, 174mm wide, 35mm deep, top open) Then, it was set in a washing machine (manufactured by Hoshizaki, JWE-680A) and washed with a detergent concentration: 0.15%, a washing time: 2 minutes (temperature: 60 ° C.), and a rinsing time: 20 seconds (temperature: 80 ° C.). Sensory evaluation was performed based on the following evaluation criteria for the degree of oil remaining on the polypropylene lunch box.
Evaluation criteria:
A: No oil droplets remain and no stickiness is felt.
○: Residual oil droplets are not observed, but a slight luster is felt.
(Triangle | delta): The residue of a slight oil droplet is recognized and a sliminess is also felt.
X: Residual oil droplets are remarkably recognized and are slimy.

<Flowability of powder composition>
A dishwasher in a transparent rectangular parallelepiped container made of acrylic resin with a length of 10 cm x width 10 cm x depth 3 cm (however, the upper surface is open and the side of the acrylic plate is pulled up) The side surface on the 10 cm × 3 cm side was opened as a discharge port and discharged naturally by gravity. The detergent composition dischargeability (flow dropability) of the powder at that time was visually observed.
◎: Very good fluid dropping property ○: Good fluid dropping property △: Not very good fluid dropping property ×: Not good fluid dropping property

<Storage stability>
500 g of the compositions of Examples and Comparative Examples were placed in a container (material: polyethylene) having a body diameter of 90 mm and a height of 108 mm, and the solidification property after being stored at 40 ° C. and 70 RH% for 6 months was visually determined.
A: Not solidified at all.
○: Almost no solidification.
Δ: Partially solidified
X: It has solidified completely.

Claims (7)

(A) 10% by mass or more of sodium metasilicate in anhydrous conversion,
(B) 10% by mass or more of sodium salt of maleic acid / acrylic acid copolymer,
(C) 5% by mass or more of sodium citrate and / or potassium citrate in anhydrous conversion,
as well as
(D) contains 25-60 mass% potassium chloride,
And the sum total of (B) and (C) component is 25 mass% or more,
A powder detergent composition for commercial automatic dishwashers, characterized in that   The powder detergent composition for a commercial automatic dishwasher according to claim 1, wherein the content of the component (A) is 12 to 14% by mass.   The powder cleaning composition for a commercial automatic dishwasher according to claim 1 or 2, wherein the content of the component (B) is 12 to 20% by mass.   Content of (C) component is 10-30 mass%, The powder cleaning composition for commercial automatic dishwashers of any one of Claims 1-3.   Content of (D) component is 30-50 mass%, The powder cleaning composition for commercial automatic dishwashers of any one of Claims 1-4.   The powder detergent composition for commercial automatic dishwashers according to any one of claims 1 to 5, wherein the sum of the components (B) and (C) is 30 to 40% by mass. Furthermore, the powder cleaning composition for business automatic dishwashers of any one of Claims 1-6 containing the nonionic surfactant (E) represented by the following formula | equation (1).
R ¹ —O— (EO) _p (PO) _q H (1)
(In the formula, R ¹ is a linear or branched hydrocarbon group having 8 to 20 carbon atoms, and p and q each independently represent a number of 1 to 6)