JP2002348594A - Solid block detergent composition and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a solid block detergent which is highly safe, is weakly alkaline with a small load on the environment, solidifies without cracks and expansion, and has excellent detergency. SOLUTION: The present invention provides (A) one or more kinds of alkali metals selected from the group consisting of carbonates, bicarbonates, silicates, phosphates, or borates, and amine compounds. 5 to 80% by weight of weak alkaline agent, (B) Chelating agent 5
A solid block detergent composition containing 80% by weight, and (C) 1 to 80% by weight of polyethylene glycol having a weight average molecular weight of 1,000 or more or a solid at ordinary temperature (25 ° C). Further, if necessary, (D) enzyme, (E)
Bleaching agents and (F) nonionic surfactants can be added.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a solid block detergent. Specifically, the present invention relates to a solid block detergent composition having high safety and low environmental load.

[0002]

2. Description of the Related Art Conventionally, automatic dishwashers have been widely used in hotels, restaurants, catering companies, hospitals, company cafeterias, and the like to efficiently wash used dishes. Further, not only foods, but also various manufacturing factories, processing factories, and the like, automatic washing machines are used to wash utensils and containers used, plastic containers used for distribution, and the like. In recent years, the use of a solid detergent has been proposed for automatic dishwashers in view of safety problems for workers due to scattering of detergent powder, and some of them have been awarded prizes. In this method, a solid detergent filled in a container such as a cartridge is attached to a washing machine, and when used, a required amount is dissolved each time with dissolving water and used for washing dishes and the like. Therefore, according to this method, there is an advantage that a high-concentration cleaning agent can be supplied at a uniform concentration in a sanitary manner. And since a compact container can be used, handling is easy, a storage space is small, and processing of the container is simple. From these advantages,
The demand for solid detergents is increasing.

Conventional solid block detergents have been commercialized by coagulation and solidification based on highly alkaline materials such as caustic soda (Japanese Patent Publication No. 59-4480). However, high alkali bases such as caustic soda have problems in terms of safety to the human body and load on the environment, and are required to be weakly alkalinized. For example, a solid block detergent based on sodium carbonate is used. Has been reported (JP-A-2000-80400, etc.). However, a detergent composition based on a weak alkaline substance is prepared by a freeze processing method (Japanese Patent Publication No.
4480, etc.), at the time of manufacture or storage,
There were problems such as expansion and cracking, poor solubility, and the inability to supply a required amount of detergent to the washer depending on supply conditions. In addition, in order to supplement the detergency of the weak alkaline base, it is necessary to mix various active aids (enzymes, bleaching components, chelating agents, etc.). There is a problem that the agent is deactivated or decomposed, and the expected effect cannot be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a weakly alkaline solid block detergent which is highly safe and has a low environmental load, and which solidifies without cracks or swelling and has excellent detergency. It is to provide a solid block detergent.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a detergent composition using a weak alkaline agent as a washing base has a certain range of molecular weight or molecular weight. The inventors have found that a solid block detergent obtained by blending polyethylene glycol having a melting point and melting and solidifying the same solves these problems, and has completed the present invention.

That is, the present invention provides, as the component (A), one or two selected from the group consisting of alkali metal carbonates, bicarbonates, silicates, phosphates or borates, and amine compounds. 5 to 80% by weight of at least one kind of weak alkaline agent,
0.1 to 80% by weight of a chelating agent as a component (B), and 1 to 80% by weight of a polyethylene glycol having a weight average molecular weight of 1000 or more or a solid at ordinary temperature (25 ° C.) as a component (C). The present invention provides a solid block detergent composition containing the same.

The present invention also provides the above solid block detergent composition wherein (A) the weak alkali agent is an anhydride of the alkali metal salt of an inorganic acid. Further, the present invention provides the above solid block detergent composition further comprising an enzyme as a component (D). Further, the present invention further comprises a bleaching agent as component (E) in an amount of from 0.1 to 3%.
The present invention provides the above solid block detergent composition containing 0% by weight and / or 0.5 to 20% by weight of a nonionic surfactant as a component (F).

[0008] The present invention also provides (A) a weak alkaline agent,
(B) A homogeneous mixture of (C) polyethylene glycol having a weight-average molecular weight of 1000 or more or a solid at room temperature (25 ° C.) together with a chelating agent and other detergent components as required. The present invention further provides a method for producing a solid block detergent composition, which comprises a step of heating and cooling until polyethylene glycol in the mixture is completely melted.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The weak alkaline agent of the component (A) used in the present invention is used as a cleaning base of a cleaning agent used in automatic dishwashers and the like, and the solid block cleaning composition of the present invention is used. The content is 5 to 80% by weight. Preferably it is 15 to 70% by weight. If the amount is less than 5% by weight, the detergency is not sufficient, and if it exceeds 80% by weight, the rinsing property deteriorates, which is not preferable.

The weak alkaline agent of the component (A) used in the present invention includes carbonates, bicarbonates, silicates and the like of alkali metals.
One or more selected from the group consisting of phosphates, borates, and amine compounds, and specifically,
Examples include sodium carbonate, potassium carbonate, sodium sesquicarbonate, sodium bicarbonate, sodium silicate, potassium silicate, dibasic sodium phosphate, sodium borate, potassium borate, ethanolamine, diethanolamine, and triethanolamine. Preferred are sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and mixtures thereof. Further, these weak alkaline agents are more preferably in the form of an anhydride containing no water of crystallization of the salt of the above-mentioned inorganic acid. An especially preferred component (A) is anhydrous sodium carbonate.

The chelating agent of the component (B) of the present invention is used in an amount of 0.1 to 80% by weight in the solid block detergent composition of the present invention.
Contained. Preferably, it is 5 to 50% by weight. 0.
If it is less than 1% by weight, sufficient detergency in hard water cannot be obtained, and if it is more than 80% by weight, the finish is poor due to poor rinsing. As the chelating agent of the component (B), various compounds which have been conventionally used and have a metal-capturing action can be used. For example, hydroxycarboxylates such as sodium malate and sodium citrate;
Aminocarboxylates such as trisodium nitrilotriacetate (NTA), sodium ethylenediaminetetraacetate (EDTA), sodium diethylenetriamipentaacetate, sodium triethylenetetraacetate, sodium hydroxyethylenediaminetriacetate; sodium pyrophosphate, sodium tripolyphosphate (STPP) Polycarboxylic acid polymers such as sodium polyacrylate, sodium polymaleate or copolymers copolymerizable therewith; 1-hydroxyethane-1,1-
Diphosphonic acid, aminotri (methylene phosphonate),
Phosphonic acids such as diethylenetriaminepenta (methylenephosphonate) and ethylenediaminetetra (methylenephosphonate) and alkali metal salts thereof; phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and alkali metal salts thereof; Can be. Preferably, sodium tripolyphosphate (STP
P), trisodium nitrilotriacetate (NTA), sodium ethylenediaminetetraacetate (EDTA), or a combination of one or more of these with a polycarboxylic acid-based polymer, or one or more of these with a phosphonate or phosphonocarboxylate Combination with acid salts and the like can be mentioned.

The polyethylene glycol (C) used in the present invention has a weight-average molecular weight of 1,000 or more or is solid at ordinary temperature (25 ° C.). If the weight average molecular weight of the polyethylene glycol is 6000 or more, the solubility of the solid block detergent using the same tends to deteriorate as the molecular weight increases.
000-6000 is more preferred. As the polyethylene glycol of the component (C), a solid form at room temperature (25 ° C.) can be used, but if it is 40 ° C. or lower, the storage stability of the solid block detergent using the same tends to deteriorate. , 65 ° C or higher, the solubility tends to be poor, so that a solid at 40 to 65 ° C is more preferable. Such a polyethylene glycol is mixed with the solid components (A) and (B) and other components to form a uniform mixture, and by heating the mixture, the polyethylene glycol is melted in the mixture and the whole is melted. By integrating and cooling, a solid block detergent having excellent solidification properties and solubility in dissolved water can be obtained.

This polyethylene glycol is contained in the solid block detergent composition of the present invention in an amount of 1 to 80% by weight. It is preferably from 10 to 30% by weight, and if it is less than 10% by weight, the moldability tends to be poor.
If the amount is more than 10% by weight, the dissolving speed of the cleaning agent tends to decrease during automatic supply to the cleaning machine, and the cleaning agent may not be supplied at a sufficient speed.

Further, the solid block detergent composition of the present invention may contain an enzyme as the component (D). The enzyme of the component (D) is contained in the solid block detergent composition of the present invention in an effective amount. For example, 0.01 to 10% by weight is preferable. (D) Examples of the component enzymes include known enzymes capable of decomposing dirt such as amylase, protease, lipase, cellulase, and pullulanase, and amylase and protease are particularly preferable.

Further, the solid block detergent composition of the present invention may contain a bleaching agent as the component (E). As an example of the component (E) bleach, a peroxygen compound is used. Examples of the peroxygen compound include an organic acid such as monoperoxyphthalate or a salt thereof, and a peroxide that generates hydrogen peroxide in an aqueous solution such as an alkali metal perborate, percarbonate, or persilicate. Can be used. Among them, sodium perborate and sodium percarbonate are particularly preferred.
The bleaching agent (E) is contained in an amount of 0.1 to 80% by weight.
The content is preferably from 1 to 10% by weight, and if it is less than 1% by weight, the bleaching performance is poor, and if it is more than 10% by weight, the finish is poor due to poor rinsing.

Further, a nonionic surfactant can be blended as the component (F) in the solid block detergent composition of the present invention. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, sucrose fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, glycerin fatty acid ester, and polyoxyethylene alkyl ether. Fatty acid esters such as glycerin fatty acid ester; coconut oil fatty acid diethanolamide (1: 1), coconut oil fatty acid diethanolamide (1: 2), lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, oleic acid Fatty acid alkanolamides such as diethanolamide and palm kernel oil fatty acid diethanolamide; alkyl glucosides; Of these, low-foaming materials such as polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene condensate of ethylenediamine, and polyoxyethylene polyoxypropylene alkyl ether are preferred. The nonionic surfactant of the component (F) of the present invention is preferably contained in the solid block detergent composition of the present invention in an amount of 0.5 to 20% by weight, more preferably 1 to 10% by weight.

Further, the solid block detergent composition of the present invention includes inorganic salts such as sodium sulfate, potassium sulfate and sodium aluminate, bleach activators, organic additives such as fragrances and dyes, high molecular carboxylic acids and the like. If necessary, a dispersing agent, a surfactant other than the nonionic surfactant, an oxidizing agent, and the like can be appropriately blended as long as the effects of the present invention are not impaired. The method for producing a solid block detergent composition according to the present invention has a weight average molecular weight of 1,000 or more, preferably 1,000, together with a weak alkaline agent (A) and a chelating agent (B) which are solid components. ~ 60
00, or solid at normal temperature (25 ° C.), preferably 40 to
A mixture of detergents is prepared by uniformly mixing polyethylene glycol which is solid at 65 ° C., and the mixture is filled in a mold container, and heated to a temperature equal to or higher than the melting point of the polyethylene glycol to melt the polyethylene glycol in the composition. Using a device capable of heating and mixing polyethylene glycol and / or a mixture of the above-mentioned detergents containing polyethylene glycol, and then heating and melting the mixture above the melting point of the polyethylene glycol separately, and then forming the container. May be used. In any case, the heating temperature needs to be higher than the melting point of polyethylene glycol, and is preferably in the range of 50C to 100C.

The above-mentioned detergent composition filled in a mold is
After being molded by applying a light force, it is cooled naturally or using a cooling device to the melting point of polyethylene glycol or less, and solidified to obtain a solid block detergent in which various detergent components are integrated. . The above-mentioned mold container may use a cartridge container for supplying a detergent such as an automatic washing machine as it is, or may solidify using an arbitrary mold container and then supply the detergent. It may be filled in a cartridge or a packaging container.

[0019]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on weight.

Example 1 Solid block detergent compositions of the present invention and comparative products were prepared according to the formulations shown in Table 1. That is, each of the detergent compositions described in Table 1 was uniformly stirred and mixed in a batch mixing tank, and then 2 kg each was filled into a 12 cmφ × 25 cm cylindrical form container. These were heated in an incubator at 70 ° C. until the polyethylene glycol in the detergent composition was completely melted. After the melting, the mold container was taken out of the incubator, which was subjected to pressure molding under a low pressure, and then allowed to cool and solidify at room temperature. After solidification, take it out of the mold container, 12cmφ × 14
cm of a solid weak alkaline detergent composition of the present invention or a comparative product having a cylindrical shape was obtained. Invention products 1 to 6 thus obtained
And, for the comparative products 1 to 3, in the solidified state by the following method,
Solubility, enzyme and peroxide stability were evaluated.

(1) Evaluation of solidification state: One molded solid block detergent was grasped with both hands, and its fragility was evaluated according to the following criteria. ◎ It cannot be broken by hand. ○ You can split a part by hand. △ The whole can be broken by hand. × Does not solidify.

(2) Solubility evaluation: Since the electric conductivity of the detergent solution is proportional to the concentration of the dissolved detergent component, the solid block washes by measuring the electric conductivity of the aqueous solution in which the detergent was dissolved. The solubility of the agent was evaluated. That is, 2 kg each of the solid block detergent compositions of the present invention product and the comparative product
Was dissolved in 100 L of tap water at 50 ° C., and the electric conductivity was measured while stirring at a speed of 100 rpm. The measuring device of the electric conductivity used is made by Mitake Electronics Co., Ltd. (MCD 1K). The time when the solid block detergent composition of the present invention or the comparative product was completely dissolved was defined as the end point of the electric conductivity, and the dissolution rate was determined by the following equation.

[0023]

(Equation 1)

The solubility of the solid block detergent was measured according to the following criteria by measuring the time until the above-mentioned dissolution rate reached 75%. ◎ Within 5 minutes ○ 5 to 10 minutes △ 10 to 15 minutes × 15 minutes or more

(3) Enzyme stability test: The solid block detergent composition obtained according to the present invention is placed in a closed container and placed in a closed container.
After storage at 60 ° C. for 60 days, the residual amounts of protease, amylase and available oxygen in the solid block detergent (stability of sodium perborate) were measured. First, the proteolytic activity of the protease was evaluated by the following method. That is, 1 ml of a 1% solution of a detergent and 5 ml of a 0.6% casein solution
And pH 10.0, 30 ℃, after reacting for 10 minutes, added 5 ml of protein precipitation reagent (TCA mixture), left at 30 ℃, 30 minutes,
Filtered. To 1 ml of the filtrate, 5 ml of a 0.55 M Na ₂ CO ₃ solution and 1 ml of a 2-fold diluted Folin reagent were added and reacted at 30 ° C. for 30 minutes. Further, the absorbance of the reaction solution at 660 nm was measured, and 3
Fo presenting 1γ l-tyrosine in the whole reaction solution at 0 ° C for 1 minute
The titer was determined with the enzyme activity giving lin coloration as one unit. Also, from this titer, the initial enzyme activity in the detergent
The residual ratio after storage at 40 ° C. for 60 days was determined as 100.

The amylolytic activity of the following amylase was evaluated by the following method. That is, 1m potato starch solution 10m
1, 1 ml of the same sample as above is added to 40 ° C., and reacted for 10 minutes. 1 ml of this reaction solution is added to a 0.1N HCl solution to stop the reaction. 10 ml of a 0.005% I ₂ -0.05% KI solution was added to 0.5 ml of this solution and reacted for 2 minutes. The absorbance was measured at 660 nm, and the iodine color value of 10 ml of 1% starch paste was measured at 40 ° C. and 1% per minute.
The reduced enzyme activity was defined as one unit. From this titer, the residual ratio after storage at 40 ° C. for 60 days was determined, taking the initial enzyme activity in the detergent as 100. The stability of each enzyme was evaluated according to the following criteria. ◎ 80 to 100% of initial enzyme activity remains ○ 60 to 80% of initial enzyme activity △ 40 to 60% of initial enzyme activity remains × 40% or less of initial enzyme activity remains

(4) Peroxide stability test: The effective oxygen content of sodium perborate in the detergent was determined by an iodine titration method. That is, 70 ml of ion-exchanged water, 1.5 ml of dilute sulfuric acid (1 + 4), and 20 ml of 10% potassium iodide were added to an appropriate amount of the sample, and the mixture was stirred for 10 minutes in a dark place, and then titrated with 0.01N NaS ₂ O ₃ to obtain available oxygen. The amount was determined. Based on this available oxygen amount, the available oxygen amount after storage at 40 ° C. for 60 days was determined based on the initial available oxygen amount in the cleaning agent as 100, and the available oxygen remaining rate was determined from this to evaluate the stability of the peroxide. The stability of the peroxide was evaluated according to the following criteria. ◎ 80 to 100% of initial available oxygen remaining ○ 60 to 80% of initial available oxygen remaining △ 40 to 60% of initial available oxygen remaining × 40% or less of initial available oxygen remaining Table 1 summarizes the results of these evaluations.

[0028]

[Table 1]

* 1: sodium tripolyphosphate * 2: trisodium nitrilotriacetic acid * 3: tetrasodium ethylenediaminetetraacetate * 4: represented by RO- (C ₂ H ₄ O) m- (C ₃ H ₆ O) nH; R is carbon number 1
2 to 14 alkyl groups, average addition mole number m is about 8, and average addition mole number n is about 5. Polyoxyethylene polyoxyfluoroperylene alkyl ether * 5: polyethylene glycol (weight average molecular weight 150
0), solid at normal temperature (25 ° C.) * 6: polyethylene glycol (weight average molecular weight 400)
0), solid at room temperature (25 ° C.) * 7: polyethylene glycol (weight average molecular weight 600
0), solid at normal temperature (25 ° C.) * 8: polyethylene glycol (weight average molecular weight 200)
00), solid at room temperature (25 ° C) * 9: polyethylene glycol (weight average molecular weight 400), liquid at room temperature (25 ° C) * 10: polyethylene glycol (weight average molecular weight 80)
0), liquid at normal temperature (25 ° C)

[0030]

The present invention is a weakly alkaline solid block detergent having high safety and low environmental load, and solidifies without cracks or swelling and has good solubility and excellent detergency. A solid block detergent can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 7/16 C11D 7/16 7/22 7/22 7/32 7/32 7/42 7/42 7 / 54 7/54 11/00 11/00 17/06 17/06 (72) Inventor Ryo Takei 7-35 Higashiogu, Arakawa-ku, Tokyo F-term in Adeka Clean Aid Co., Ltd. 4H003 AC08 AC23 BA01 BA10 CA15 DA19 EA08 EA12 EA15 EA16 EA18 EB13 EB15 EB16 EB36 EC01 EC02 ED02 EE05 FA02 FA03 FA23 FA28 FA32 FA42

Claims (6)

[Claims] (A) one or more weak alkali agents selected from the group consisting of carbonates, bicarbonates, silicates, phosphates or borates of an alkali metal, and amine compounds 5 to 80% by weight, (B) 0.1 to 80% by weight of a chelating agent, and (C) 1 to 80% by weight of polyethylene glycol having a weight average molecular weight of 1,000 or more or solid at ordinary temperature (25 ° C.). A solid block detergent composition. 2. The solid block detergent composition according to claim 1, wherein (A) the weak alkaline agent is an anhydride of the alkali metal salt of the inorganic acid. 3. The solid block detergent composition according to claim 1, further comprising (D) an enzyme. 4. Further, (E) 0.1 to 30% by weight of a bleaching agent and / or (F) 0.5 to 2% of a nonionic surfactant.
The solid block detergent composition according to any one of claims 1 to 3, which contains 0% by weight. 5. The solid block detergent composition according to claim 1, wherein (A) the weak alkaline agent is anhydrous sodium carbonate. 6. Granules having a weight-average molecular weight of 1,000 or more or a solid at room temperature (25 ° C.) together with (A) a weak alkali agent, (B) a chelating agent and other detergent components as required. , A method for producing a solid block detergent composition, comprising the steps of: uniformly mixing block-like or flake-like polyethylene glycol, heating the mixture until the polyethylene glycol in the mixture is completely melted, and then cooling.