JP4907199B2 - Method for producing powder detergent composition for dishwasher - Google Patents

Description

  The present invention relates to a method for producing a powder detergent composition for a dishwasher.

  A dishwasher is a facility for washing dishes such as dirty dishes, glasses and cooking utensils, and is used in kitchens such as homes, restaurants and coffee shops. Dishwashing is usually performed in the order of washing process-rinsing process, and the washing process uses a non-foaming or low-foaming dishwasher cleaning composition different from the dishwashing composition for hand washing. Yes.

  Examples of the form of the detergent composition for a dishwasher include liquid, solid and powder. In the case of a liquid detergent composition, in a kitchen such as a restaurant or a coffee shop where the number of washings is large, the liquid is supplied to the washing tank by an automatic supply device using a pump. However, since there are few active ingredients, the usage-amount of a liquid cleaning composition increases, and the heavy thing contained in the big polyethylene container about 20L is used. Therefore, the replacement work of the liquid detergent composition is heavy labor and requires a large installation place. Furthermore, since polyethylene containers are flame retardant and biodegradable, there is a problem of disposal.

  In the case of a solid detergent composition, in a kitchen such as a restaurant or coffee shop where the number of washings is high, set the solid detergent composition contained in a container such as plastic in a hopper dedicated for commercial dishwashers and spray water or hot water. The solid cleaning composition is sprayed by a shower or the like, and the dissolved cleaning solution is supplied into the cleaning tank by an automatic supply device. However, the solid detergent composition is poorly soluble and cannot be dissolved in a short time in the initial stage of supply, and the concentration of the cleaning liquid may be insufficient to stop the commercial dishwasher.

  Powder cleaning compositions have been developed to improve solubility. At home, a powder detergent composition is generally used, and a necessary amount of a powder detergent composition for a dishwasher contained in a container such as plastic is directly put into a commercial dishwasher. In kitchens such as restaurants and coffee shops, set the powder detergent composition in a hopper dedicated for commercial dishwashers, spray water or hot water onto the powder detergent composition with a spray or shower, etc. It is supplied to the washing tank with an automatic feeder. Alternatively, the powder cleaning composition filled in a pouch container or the like is transferred to a dedicated hopper for commercial dishwashers, and water or warm water is sprayed onto the powder cleaning composition by spraying or showering to dissolve the cleaning solution Is supplied to the cleaning tank by an automatic supply device.

In order to produce a powder cleaning composition for a dishwasher, an ordinary mixing apparatus is used. For example, a ribbon mixer, a paddle mixer, a nauter mixer, a V-type mixer, a W-type mixer, and the like can be given. In general, in order to uniformly mix a powdery water-soluble polymer compound with a raw material at room temperature, it is preferable to mix the polymer compound with the powder component as it is. However, when mixing an aqueous material containing a water-soluble polymer compound with a powder component, it is very difficult to maintain powder fluidity, and the powder mixture adheres to the inner wall of the mixing device due to dissolution or viscosity increase. Thus, uniform mixing cannot be performed. Therefore, a method has been performed in which water is previously evaporated and then the water-soluble polymer compound is mixed, or an aqueous solution containing the water-soluble polymer compound is mixed while heating the mixing device to evaporate the water. In addition, a method of evaporating moisture by spraying in a drying tower in a state where an aqueous solution containing a water-soluble polymer compound and an inorganic powder compound are mixed is performed. However, these methods have high energy costs, and there is a concern that the powder mixture is denatured by heating. Furthermore, blocking and caking are likely to occur during storage. As a method for adding a liquid component without using an aqueous solution, for example, in Patent Document 1, there is a method for producing a powder detergent composition for a dishwasher in which a nonionic surfactant, which is a fluid liquid, is dividedly added to builders having different particle sizes. It is disclosed.
Japanese Patent Laid-Open No. 10-195482

  Patent Document 1 does not mention that an aqueous solution of a water-soluble polymer compound is mixed with a powder component to produce a composition. The problem of the present invention is that in the method of mixing an aqueous solution containing a water-soluble polymer compound with a powder component, uniform mixing is possible without the powder mixture adhering to the inner wall surface of the mixing apparatus due to dissolution or increase in viscosity at the time of manufacture. Another object of the present invention is to provide a method for producing a powder detergent composition for a dishwasher, wherein the obtained composition has good powder flowability and excellent storage stability.

  The present invention relates to a powdery organic polymer compound having water absorption by hydrogen bonding, an organic powder compound capable of incorporating free water as crystallization water, and a water-soluble inorganic compound capable of incorporating free water as crystallization water. A water-soluble polymer compound containing one or more cationic monomers as structural units while stirring one or more powder compounds (A) selected from the group consisting of powder compounds (hereinafter referred to as component (A)) (B) Dishwashing comprising the step (I) of adding an aqueous solution containing [B) component (hereinafter referred to as component (B)) to incorporate water in the aqueous solution into component (A) by hydrogen bonding or crystal water The present invention relates to a method for producing a machine powder cleaning composition. Here, the water-soluble inorganic powder compound refers to a compound having a solubility in 100 g of water of 1 g or more at 25 ° C.

  According to the present invention, in the step of incorporating water in an aqueous solution containing a water-soluble polymer compound into the powder compound, the powder mixture can be uniformly mixed without adhering to the inner wall surface of the mixing device due to dissolution or viscosity increase. In addition, a method for producing a powder detergent composition for a dishwasher having good powder fluidity and excellent storage stability is provided.

<(A) component>
Among the component (A) used in the present invention, as an organic polymer compound in a powder having water absorption by hydrogen bonding, dextrin, carrageenan, xanthan gum, guar gum, pectin, locust bin gum, or derivatives thereof, modified starch, Examples thereof include polysaccharides such as methylcellulose and carboxymethylcellulose, and synthetic polymer compounds such as polyvinyl alcohol, polyacrylate, polyacrylamide, and polyethylene oxide. In addition, among the component (A) used in the present invention, examples of the organic powder compound capable of incorporating free water as crystallization water include citric acid, tartaric acid, malic acid, and salts thereof. Anhydrides and hydrates are preferred. From the viewpoint of powder flowability, it is preferably at least one selected from dextrin and derivatives thereof, methylcellulose and derivatives thereof, carboxymethylcellulose and derivatives thereof, modified starch, and citrate, and more preferably modified starch, Acid salt. Specific examples include oxidized starch, sodium starch octenyl succinate, and sodium citrate.

  The powdery organic polymer compound having water absorption by hydrogen bonding preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 5,000 to 5,000,000, and still more preferably 10,000. 000 to 3,000,000, particularly preferably 10,000 to 1,000,000.

  Among the components (A) used in the present invention, examples of water-soluble inorganic powder compounds that can take in free water as crystallization water include carbonates, phosphates, silicates, sulfates, borates, and the like. These anhydrides and hydrates are preferable. From the viewpoint of powder fluidity, it is preferably at least one selected from carbonates, phosphates, silicates and sulfates, more preferably phosphates and sulfates. Specific examples include sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium sulfate and the like.

<(B) component>
As the monomer used for constituting the monomer unit (a) of the component (B), one or more selected from the compounds of the following general formula (1) and the compounds of the general formula (2) are preferable.

[Wherein, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. Examples of the anion of Z ⁻ include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. Can be mentioned. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

  Specifically preferred as the compound of the general formula (1) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, acryloyl. (Or methacryloyl) oxyalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, N- (ω-alkenyl (C2-10))-N , N, N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, N, N-di (ω-alkenyl (carbon number 2 to 10))-N, N-dialkyl (carbon number 1 to 3) 4 A quaternary ammonium salt is preferred, and diallyldimethylammonium salt is particularly preferred.

  Particularly preferred as the compound of the general formula (2) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N-dialkyl (C1-3) amine, acryloyl (or methacryloyl) oxyalkyl. (C1-5) -N, N-dialkyl (C1-3) amine, N- (ω-alkenyl (C2-10))-N, N-dialkyl (C1-3) amine N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine and diallylamine are preferable, and allylamine and diallylmethylamine are particularly preferable. , Diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, acryloyl (or methacryloyl) oxy Ethyl-N, N-dimethylamine is good.

  From the viewpoint of surface adsorption power, the component (B) is 10 to 99 mol%, preferably 30 to 90 mol%, more preferably 50 to 90 mol%, particularly preferably the monomer unit (a) with respect to all monomer units. 60 to 80 mol% is contained. This mol% is calculated by [number of moles of monomer unit (a) / number of moles of all monomer units] × 100.

The component (B) preferably has a monomer unit (b) represented by —SO ₂ —. As a method for introducing such a monomer unit into the polymer, a predetermined amount of SO ₂ gas is blown into a solution containing the compound of the general formula (1) and / or the compound of the general formula (2), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisisobarrel nitrilo, 2,2'-azobis (2-amidinopropane), t-butyl hydroperoxide, cumene hydroper It can be obtained by polymerization using a polymerization initiator selected from oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfate, and hydrogen peroxide. A solvent can be used at the time of polymerization. Specifically, alcohols selected from water, methanol, ethanol and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazo Lydinone, acetonitrile, propionitrile, toluene, xylene and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably -20 to 200 ° C, preferably -10 to 100 ° C. In the present invention, it is possible to polymerize with light or radiation, and it is possible to polymerize efficiently by irradiating light with a wavelength of 300 to 450 nm.

  From the viewpoint of finish, the molar ratio of monomer unit (b) / monomer unit (a) is preferably 0.01 to 1, more preferably 0.03 to 0.75, still more preferably 0.05 to 0.5. It is.

  The component (B) can be included as a structural unit derived from an anionic monomer (hereinafter referred to as a monomer unit (c)). In this case, the molar ratio of the monomer unit (a) to the monomer unit (c) Unit (a) / monomer unit (c) = 10/90 to 90/10, further 30/70 to 90/10, more preferably 50/50 to 80/20, and particularly preferably 50/50 to 70/30. . Examples of the anionic monomer include monomers selected from the following (i).

  (I) Acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonic acid Compound selected from salt, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (C1-12)

  Moreover, (B) component can also be included as a structural unit derived from a nonionic monomer [henceforth a monomer unit (d)]. Examples of the nonionic monomer include monomers selected from the following (ii) to (iv).

  (Ii) Acrylic (or methacrylic) amide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic) Acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound

  (Iii) Acrylic acid (or methacrylic acid) alkyl (1 to 5 carbon atoms), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (1 carbon atom) -5), ester group-containing compound selected from vinyl acetate

  (Iv) ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl Olefin compounds selected from -1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene

  Among these, from the viewpoint of finish, a monomer unit derived from the monomer (i) or (ii) is particularly preferable, and a monomer unit derived from the monomer (i) is most preferable. Among these, acrylic acid or its sodium salt or Preference is given to potassium salt, methacrylic acid or its sodium or potassium salt, maleic acid or its sodium or potassium salt. Here, the counter ion of the monomer unit derived from the monomer (i) may be a cationic group portion of the polymer to be contained.

  When the component (B) has a monomer unit (d), the molar ratio of the monomer unit (d) / monomer unit (a) is 0.05 to 1, more preferably 0.1 to 0.00 from the viewpoint of finish. 75, especially 0.2 to 0.5 is preferred.

  Component (B) preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 1,000 to 3,000,000, still more preferably 1,000 to 1,000,000, and particularly preferably. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance with a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent.

  In the component (B) used in the present invention, the monomer unit (a) and any monomer units (b), (c), (d) are present in either the main chain or the side chain in the polymer. It doesn't matter. These may be randomly polymerized, block polymerized, or graft polymerized. In the present invention, it is most preferable to use a polymer composed only of the monomer unit (a), the monomer unit (b) and the monomer unit (c) as the component (B).

<Method for producing powder cleaning composition for dishwasher>
In the production method of the present invention, the aqueous solution containing the component (B) [hereinafter referred to as the (B) aqueous solution] is added to the component (A) by adding the aqueous solution containing the component (B) while stirring the component (A). It has process (I).

  The concentration of the component (B) in the aqueous solution (B) is preferably 0.1 to 90% by weight, more preferably 1 to 70% by weight, and still more preferably 5 to 50% by weight, from the viewpoint of the viscosity of the aqueous solution (B). Particularly preferred is 10 to 40% by weight.

  When (B) aqueous solution is added to (A) component, from the viewpoint of powder flowability and storage stability, the weight ratio of (B) aqueous solution / (A) component is preferably 0.001 to 0.5. Preferably it is 0.005-0.4, More preferably, it is 0.01-0.4, Most preferably, it is 0.03-0.3.

  The method for adding the aqueous solution (B) to the component (A) may be continuous addition, intermittent addition, or batch addition, but continuous addition by dropping is preferred.

  Moreover, as temperature conditions when (B) aqueous solution is added to (A) component, it is low temperature (for example, -20 degreeC or more and less than 10 degreeC), high temperature (for example, 40-100 degreeC), or room temperature (for example, 10 degreeC or more-40 degreeC). However, when an exothermic reaction occurs and the temperature rises rapidly, it is necessary to cool the mixing apparatus and keep the powder temperature at a low temperature. Further, in order to maintain the powder fluidity, the mixing apparatus may be heated to increase the powder temperature.

  The temperature condition for producing a uniform powder detergent composition for a dishwasher may be any of the above-mentioned low temperature, high temperature or room temperature, but if an exothermic reaction occurs and the temperature rises severely, the mixing device is cooled. Thus, it is necessary to keep the powder temperature low. Further, in order to maintain the powder fluidity, the mixing apparatus may be heated to increase the powder temperature.

  Moreover, as addition rate of (B) aqueous solution when adding (B) aqueous solution continuously with respect to 1 kg of (A) component, Preferably it is 0.001-10 kg / min, More preferably, it is 0.005-5 kg / min. Min, more preferably 0.01-2 kg / min, particularly preferably 0.02-1 kg / min.

  The total mixing time for producing a uniform powder detergent composition for dishwashers is preferably 5 to 360 minutes, more preferably 5 to 240 minutes, and even more preferably 10 to 180 minutes. Particularly preferably, it is 10 to 90 minutes.

  In the present invention, step (I) can be carried out in the presence of a water-insoluble inorganic powder compound from the viewpoint of surface modification and storage stability. Here, the water-insoluble inorganic powder compound means one having a solubility in 100 g of water of less than 1 g at 25 ° C. The primary particle diameter of the water-insoluble inorganic powder is preferably 5 nm to 200 μm, more preferably 20 nm to 100 μm, and still more preferably 20 nm to 50 μm, from the viewpoints of surface modification and storage stability. Specifically, crystalline silicate, aluminosilicate, silica, and alumina are preferable. The content of the water-insoluble inorganic powder compound is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, still more preferably 0.1 to 6% by weight, from the viewpoint of storage stability. %, Particularly preferably 0.5 to 5% by weight.

When silica is used as the water-insoluble inorganic powder compound, it is preferable to use Aerosil (manufactured by Nippon Aerosil Co., Ltd.); Toxeal, Fine Seal, Leorosil [manufactured by Tokuyama Co., Ltd.]; .

  In addition, in order to age or cool the mixture obtained in step (I) or a mixture obtained by adding other components to the mixture or the obtained powder detergent composition for a dishwasher, it is allowed to stand for a certain period of time. Also good. The standing time is preferably 1 to 72 hours, more preferably 3 to 48 hours, still more preferably 5 to 36 hours, and particularly preferably 5 to 24 hours.

  In order to obtain a uniform powder detergent composition for a dishwasher, the step (II) of pulverizing the mixture obtained in step (I) or a mixture obtained by adding other components to the mixture may be performed. Preferably, the temperature condition may be a low temperature (for example, −20 ° C. or more and less than 10 ° C.), a high temperature (for example 40 to 100 ° C.), or a room temperature (for example, 10 ° C. or more and less than 40 ° C.). When it is intense, it is necessary to cool the mixing device and keep the powder temperature low. Further, in order to maintain the powder fluidity, the pulverizer may be heated to pulverize the powder at a high temperature.

  The pulverization time in the step (II) is preferably 0.5 to 25 hours, more preferably 1 to 12 hours, still more preferably 1 in order to obtain a uniform powder detergent composition for dishwashers per ton. -8 hours, particularly preferably 1 to 6 hours.

  A normal pulverizer is used for pulverization in the step (II). Examples thereof include a vertical roller mill, a centrifugal roller mill, a vibration mill, a rod mill, a power mill, a hammer mill, a jet mill, a ball mill, a planetary ball mill, a comb mill, and a Fitz mill.

  The component (A) is mixed with the aqueous solution (B) while stirring. A mixing device can be used for stirring the component (A) and mixing the component (A) and the aqueous solution (B). For example, a ribbon mixer, a paddle mixer, a Nauter mixer, a V-type mixer, a W-type mixer, a high speed mixer, a Redige mixer, a Henschel mixer, and the like can be given.

  By mixing the aqueous solution (B) with the component (A) as described above, water in the aqueous solution (B) is taken into the component (A), and the mixture exhibits a powder-like appearance and physical properties. It will be excellent. In the step (I), it is preferable that substantially all of the water in the aqueous solution (B) is taken into the component (A).

  The powder mixture obtained in the step (I) preferably has fluidity capable of uniform mixing without adhering to the inner wall surface of the mixing apparatus.

  The detergent composition for a dishwasher obtained according to the present invention was prepared from a measuring device for apparent density according to JIS K 3362, which was placed on a stable table and adjusted horizontally. The flow-down time is preferably 30 seconds or less, more preferably 20 seconds or less, still more preferably 15 seconds or less, and particularly preferably 10 seconds or less.

  The powder detergent composition for a dishwasher obtained by the present invention contains 0.01 to 10% by weight, more preferably 0.05 to 5% by weight of the component (B) from the viewpoint of finish. Furthermore, it is preferable to contain 0.1 to 3% by weight, particularly 0.2 to 2% by weight. In order to be within this range, the concentration of (B) component in the aqueous solution, (A) component and mixing ratio, etc. It is preferable to adjust.

  Moreover, it is preferable that the powder cleaning composition for tableware washing machines obtained by this invention contains a nonionic surfactant. The nonionic surfactant is not particularly limited, but glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy Examples include ethylene alkyl ether, polyoxyethylene dialkyl ether, polyoxyethylene glycol, polyoxyethylene oxypropylene glycol, and polyoxypropylene oxyethylene oxypropylene glycol.

From the viewpoint of detergency, a nonionic surfactant represented by the following general formula (3) is preferably used.
^{R 14 - (AO) n-} R 15 (3)
[Wherein, R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, preferably a hydrogen atom, a linear or branched carbon group having 6 to 18 carbon atoms. More preferably, it is a hydrogen atom, linear or branched C8-14. n is an average added mole number, and is a number of 1-500, Preferably it is 1-400, More preferably, it is 1-350, More preferably, it is a number of 1-200, Most preferably, it is a number of 1-100. AO is the same or different and is an ethylene group, a propylene group or a butylene group, preferably an ethylene group or a propylene group. ]

  Furthermore, from the viewpoints of detergency, non-foaming property and low-foaming property, one kind selected from the nonionic surfactant represented by the general formula (4) and the nonionic surfactant represented by the general formula (5) The above is preferable.

HO (CH ₂ CH ₂ O) _a (CH (CH ₃ ) CH ₂ O) _b (CH ₂ CH ₂ O) _c H (4)
HO (CH (CH ₃ ) CH ₂ O) _d (CH ₂ CH ₂ O) _e (CH (CH ₃ ) CH ₂ O) _f H (5)
[Wherein, a, b, c, d, e and f are the average number of moles added, each independently a number of 1 to 350. ]

  In the general formulas (4) and (5), a, b, c, d, e and f are the average added moles of ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO). Yes, each independently a number from 1 to 350.

  The nonionic surfactant component of the general formulas (4) and (5) preferably contains 10 mol% or more of EO in the total of EO and PO, and a, b, c, It is preferable to select d, e, and f.

  Further, the weight average molecular weight of the nonionic surfactant component represented by the general formulas (4) and (5) is preferably 1,000 to 15,000, and more preferably 1,500 to 6,000. Nonionic surfactant components of the general formulas (4) and (5) are available from BASF under the trade names of “Pluronic” and “Pluronic R”. As the nonionic surfactant component of the general formulas (4) and (5), the nonionic surfactant of the general formula (5) is preferable from the viewpoint of low foamability.

  From the viewpoint of detergency, the nonionic surfactant is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight in the powder detergent composition for a dishwasher of the present invention. More preferably 0.1 to 20% by weight. Particularly preferably, it is contained in an amount of 0.5 to 10% by weight. The addition method of the nonionic surfactant may be any of continuous addition, intermittent addition, or batch addition, but continuous addition is preferred. The timing of addition is not particularly limited, but is preferably after step (I) from the viewpoint of powder flowability.

<Other ingredients>
The powder detergent composition for dishwashers obtained by the present invention comprises an enzyme, an oxygen bleach, an anionic surfactant, an amphoteric surfactant, a corrosion inhibitor, an antifoaming agent, a solvent, a hydrotrope agent and the like. Can be contained. These can refer to those described in International Publication No. 99/58633 pamphlet.

Example 1
3 kg of sodium tripolyphosphate was added to a 20 L Nauter mixer, and 0.9 kg of an aqueous solution containing 25% by weight of the water-soluble polymer compound (B1) shown in Table 1 was added dropwise over 2 minutes while stirring. After stirring the Nauter mixer for 10 minutes while cooling the powder temperature to 80 ° C. or less, 6 kg of potassium carbonate, 0.15 kg of nonionic surfactant (Pluronic RPE2520 manufactured by BASF), and acrylic acid / maleic acid 0.45 kg of copolymer and sodium salt (Sokalan CP5 Granules manufactured by BASF) was added and stirred for 10 minutes. The obtained powder mixture was allowed to stand for 12 hours and then pulverized for 5 minutes by a power mill. The pulverized powder mixture was returned to a 20 L Nauter mixer, 4.5 kg of potassium silicate was added, and the mixture was stirred for 10 minutes to obtain 15 kg of a powder cleaning composition for a dishwasher of Example 1 shown in Table 1.

Example 2
In the production method shown in Example 1, except that the aqueous solution containing 40% by weight of the water-soluble polymer compound (B2) was used instead of the aqueous solution of the water-soluble polymer compound (B1), the examples shown in Table 1 were used. Thus, 15 kg of a powder cleaning composition for dishwasher 2 was obtained.

Example 3
To 20 L Nauter mixer, 1.5 kg of anhydrous sodium sulfate, 1.5 kg of sodium citrate dihydrate and 1.5 kg of oxidized starch (Lactway 2 manufactured by Matsutani Chemical Co., Ltd.) were added, and the aqueous solutions shown in Table 1 were stirred. 0.9 kg of an aqueous solution containing 25% by weight of the functional polymer compound (B1) was added dropwise over 2 minutes. After stirring for 15 minutes at room temperature, 6 kg of potassium carbonate, 0.15 kg of nonionic surfactant (Pluronic RPE2520 manufactured by BASF), and 0.45 kg of acrylic acid / maleic acid copolymer, sodium salt (Sokalan CP5 Granules manufactured by BASF) In addition, the mixture was stirred for 15 minutes. Further, 3 kg of potassium silicate was added and stirred for 15 minutes to obtain 15 kg of a powder cleaning composition for a dishwasher of Example 3 shown in Table 1.

Example 4
In the production method shown in Example 3, except that an aqueous solution containing 40% by weight of the water-soluble polymer compound (B2) was used instead of the aqueous solution of the water-soluble polymer compound (B1), the examples shown in Table 1 were used. Thus, 15 kg of a powder cleaning composition for dishwasher No. 4 was obtained.

Example 5
Add 20 kg of anhydrous sodium sulfate and 1.5 kg of sodium citrate dihydrate to a 20 L Nauter mixer and add 0.24 kg of an aqueous solution containing 25% by weight of the water-soluble polymer compound (B1) shown in Table 1 while stirring. Was added dropwise over 1 minute. After stirring at room temperature for 10 minutes, 2 kg of potassium carbonate, 3.5 kg of sodium percarbonate, 1.46 kg of potassium silicate, and 0.2 kg of acrylic acid / maleic acid copolymer, sodium salt (BASF Sokalan CP5 Granules) were added to add 5 kg. Stir for minutes. Furthermore, 0.1 kg of starch-degrading enzyme (Termamyl Mill 60T manufactured by Novo Nordisk Bioindustry) was added and stirred for 5 minutes to obtain 15 kg of a powder cleaning composition for a dishwasher of Example 5 shown in Table 1. .

Example 6
In the production method shown in Example 5, except that the aqueous solution containing 40% by weight of the water-soluble polymer compound (B2) was used instead of the aqueous solution of the water-soluble polymer compound (B1), the examples shown in Table 1 were used. Thus, 15 kg of a powder cleaning composition for dishwasher 6 was obtained.

Example 7
In the production method shown in Example 4, except that a part of anhydrous sodium sulfate was replaced with the water-insoluble inorganic powder compound 1, 15 kg of the powder cleaning composition for a dishwasher of Example 7 shown in Table 1 was used. Obtained.

Example 8
In the production method shown in Example 6, except that a part of anhydrous sodium sulfate was replaced with the water-insoluble inorganic powder compound 1, 15 kg of the powder cleaning composition for dishwasher of Example 8 shown in Table 1 was used. Obtained.

Comparative Examples 1-2
In the production method shown in Example 1, except that sodium chloride (free water cannot be taken in as crystallization water) as a powder compound instead of the component (A), Comparative Examples 1 and 2 shown in Table 1 were used. 15 kg of a powder cleaning composition for a dishwasher was obtained.

Comparative Examples 3-4
In the production method shown in Example 3, except that sucrose (organic low molecular weight compound, free water cannot be taken in as crystallization water) is used as a powder compound instead of the component (A), the results are shown in Table 1. 15 kg of the powder cleaning composition for tableware washing machines of Comparative Examples 3 to 4 was obtained.

<Evaluation>
When preparing the powder detergent composition for a dishwasher of Table 1 according to the above examples and comparative examples, the evaluation of the adhesion state to the inner wall surface of the mixing apparatus, powder flowability and storage stability was as follows. Went in the way. The results are shown in Table 1.

(1) Adhesion state of the inner wall surface of the mixing device (B) In the step of incorporating water in the aqueous solution containing the component into the (A) component, the adhering state of the powder mixture (before pulverization) to the inner wall surface of the mixing device The evaluation criteria were as follows.
* Adhesion state ◎: Adhesion is not observed at all, and uniform mixing is possible. ○: Slight adhesion is observed, but uniform mixing is possible. Δ: Adherence is clearly recognized, and it is necessary to perform uniform mixing while dropping the adhering. Adhesion is recognized and uniform mixing is impossible.

  The results of the adhesion state are shown in Table 1. It became clear that the powder mixture obtained by the production method of the present invention has little adhesion to the inner wall surface of the mixing apparatus and can be mixed uniformly.

(2) Powder flowability An apparent density measuring instrument described in JIS K 3362 was placed on a stable table and adjusted horizontally. With the damper of this measuring device closed, 100 mL of a powder cleaning composition for dishwashing was added. The damper was fully opened, and the time for 100 mL of the dishwashing powder cleaning composition to flow down was measured.

  The results of powder flowability are shown in Table 1. It was revealed that the powder detergent composition for dishwashers obtained by the production method of the present invention is excellent in powder flowability.

(3) Storage stability 1 kg of the powder cleaning composition for dishwashing was added to a plastic 2 L container and sealed. The powder flowability of the dishwashing powder cleaning composition stored for 1 month in an environment of temperature 40 ° C. and humidity 50% RH was measured by the method described above.

  The results of the powder fluidity of the stored products are shown in Table 1. It was revealed that the powder detergent composition for dishwashers obtained by the production method of the present invention is excellent in storage stability.

(note)
* 1: Oxidized starch (Lactway 2 manufactured by Matsutani Chemical Co., Ltd.)
* 2: 25% by weight aqueous solution of a copolymer of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 70/25/5) [water-soluble polymer compound (B1)] (molecular weight about 20,000) * 3: chloride A 40% by weight aqueous solution of a copolymer of diallyldimethylammonium and acrylic acid (molar ratio 64/36) [water-soluble polymer compound (B2)] (Merquat280, manufactured by Calgon, molecular weight of about 450,000) * 4: PO · EO · PO block polymer, Pluronic RPE2520 (BASF)
* 5: Acrylic / maleic acid copolymer, sodium salt, Sokalan CP5 Granules (BASF)
* 6: Termamyl 60T, Novo Nordisk Bioindustry Co., Ltd.
* 7: Toku Seal, manufactured by Tokuyama Corporation

Claims (10)

Dust and its derivatives, methylcellulose and its derivatives, carboxymethylcellulose and its derivatives, and modified starch , organic polymer compound (A1) in powder form having water absorption by hydrogen bonding, citric acid, tartaric acid, From at least one organic powder compound (A2) capable of taking in free water as crystal water selected from malic acid and salts thereof, and carbonates, phosphates, silicates, and sulfates One or more powder compounds (A) selected from the group consisting of one or more water-soluble inorganic powder compounds (A3) capable of taking in free water as crystal water and water-insoluble inorganic powder compounds while stirring the door,
An aqueous solution containing a water-soluble polymer compound (B) containing a monomer unit (a) having at least one group selected from an amino group and a quaternary ammonium group at a concentration of 5 to 50% by weight. By adding the compound (A) = 0.001 to 0.5 in a weight ratio ,
A step (I) of incorporating water in the aqueous solution into the powder compound (A) by hydrogen bonding or as crystal water;
A method for producing a powder detergent composition for a dishwasher. The manufacturing method of Claim 1 whose water-insoluble inorganic powder compound is 1 or more types of compounds chosen from crystalline silicate, an aluminosilicate, a silica, and an alumina . The manufacturing method of Claim 1 or 2 which has the process (II) which grind | pulverizes the mixture obtained by the process (I), or the mixture which added another component to this mixture . The manufacturing method of Claim 3 which performs process (II) on the temperature conditions of -20 degreeC-100 degreeC. The production method according to claim 3 or 4, wherein the pulverization time in step (II) is 0.5 to 25 hours per ton of the mixture. Water-soluble polymeric compound monomer units (B) (a) is any claim 1-5 derived from a compound represented by the compound represented by the following general formula (1) and / or formula (2) The manufacturing method of Claim 1.

[Wherein, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ] The water-soluble polymer compound (B) includes a monomer unit (b) represented by —SO ₂ —, and the monomer unit (b) / monomer unit (a) molar ratio is 0.01 to 1. The manufacturing method of any one of Claims 1-6 . The powder compound (A) is an organic polymer compound of powder having water absorption by hydrogen bonding, one or more selected from dextrin and derivatives thereof, methylcellulose and derivatives thereof, carboxymethylcellulose and derivatives thereof, and modified starch including method of any one of claims 1-7. The production according to any one of claims 1 to 8 , wherein the powder compound (A) comprises at least one organic powder compound selected from citrate capable of taking in free water as crystal water. Method. The powder compound (A) includes one or more water-soluble inorganic powder compounds capable of taking in free water as crystallization water selected from carbonates, phosphates, silicates, and sulfates. any one method according to 1-9.