JP5616759B2 - Granular detergent and method for producing granular detergent - Google Patents

Description

The present invention relates to a granular detergent and a method for producing the granular detergent.

Conventionally, detergents containing surfactants such as nonionic surfactants, chlorine agents and the like are known as detergents used for washing dishes using an automatic dishwasher.
It is also known that such a cleaning agent can be supplied to an automatic dishwasher using an automatic supply device.

As the cleaning agent, for example, Patent Document 1 discloses a cleaning agent for an automatic dishwasher having sodium hydroxide and the like, orthosilicate, sodium tripolyphosphate, and sodium metasilicate pentahydrate as essential components. It is disclosed.
The cleaning agent described in Patent Document 1 is produced by mixing powders of components having a particle size of about 1 mm, and is in a powder form.

On the other hand, as an automatic supply device for a cleaning agent, Patent Document 2 discloses a reservoir that stores a cleaning agent, a screw that is provided in a lower portion of the reservoir, and a screw that transfers the cleaning agent, and the transferred cleaning agent is mixed with water. The automatic supply apparatus provided with the mixing part which prepares cleaning agent aqueous solution by this, and the supply part which supplies cleaning agent aqueous solution to an automatic dishwasher is disclosed.

JP 09-272896 A JP 2002-320584 A

When the powdery cleaning agent described in Patent Document 1 is used in the automatic supply apparatus described in Patent Document 2, the powdery cleaning agent has a particle size that is too small and has low fluidity, and the cleaning agent is contained in the reservoir. However, a dome-shaped cavity is formed, and the problem of poor supply that the entire amount is not conveyed by the screw occurs. In particular, if the powdery cleaning agent absorbs water in a state where a dome-shaped cavity is formed, the cleaning agent is likely to solidify, and the problem of supply failure becomes significant.
Further, it has been known that when the particle size of the powder is small, it easily adheres to the apparatus and causes supply failure. Further, when the particle size of the powder is small, there is a problem that an operator handling the cleaning agent is easily peeled off by the scattered powder.

In order to solve such a problem, the present inventors tried to prevent the powdery cleaning agent from solidifying by periodically applying vibration to the reservoir. It was difficult to always supply a homogeneous cleaning agent.

Moreover, although the present inventors tried to make it difficult to classify the powder of each component by making the particle size of each component of the powdery cleaning agent uniform, it was difficult to suppress the classification.
Thus, it is difficult to solve the supply failure with the conventional powdery cleaning agent.

Furthermore, when the present inventors added a powdery chlorine agent as a bleaching component to a cleaning agent containing a nonionic surfactant, the component decomposes due to contact between the nonionic surfactant and the chlorine agent, It has been found that detergency is reduced.

The present invention has been made to solve the above-described problems, can be supplied by an automatic supply device, and can suppress decomposition due to contact between a nonionic surfactant and a chlorine agent. An object is to provide a granular detergent.

That is, the granular detergent of the present invention comprises a granular composition containing a granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and a binder,
A granular cleaning agent comprising a chlorine agent,
The binder contains sodium silicate.

Since the granular cleaning agent of the present invention contains a granular composition that is not in powder form, it is excellent in fluidity.
The granular detergent of the present invention contains a granular composition containing granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and sodium silicate as a binder. Because the sodium silicate binder is sufficiently high in viscosity, the above granular composition makes the granular orthosilicate adsorbed with the liquid nonionic surfactant and the chelating agent stronger with sodium silicate. Can be glued.
For this reason, even if the granular composition and the chlorine agent come into contact with each other and the surface of the granular composition is rubbed when vibration is applied during storage in the reservoir, screw transportation, handling, etc. It is hard to generate powder.
In addition, sodium silicate as a binder covers the periphery of granular orthosilicate and chelating agent to form a film with a property close to glassy, so that the granular composition is difficult to adhere to the wall surface of the automatic feeder. Become.
Therefore, the granular cleaning agent of the present invention is less likely to cause poor supply even when an automatic supply device is used. Moreover, since it is hard to generate | occur | produce a powder, it is prevented that an operator shows off by suction | attraction of powder.

In addition, since the liquid nonionic surfactant is blended in the granular composition in a state where it is adsorbed to the granular orthosilicate, the contact between the chlorinating agent and the nonionic surfactant is reduced. Decomposition of nonionic surfactants and the like can be suppressed.
Therefore, the granular cleaning agent of the present invention can maintain good cleaning power for a long period of time.

In the granular cleaning agent of the present invention, the binder preferably contains sodium silicate hydrate or an aqueous sodium silicate solution.

In the granular cleaning agent of the present invention, the molar ratio of Na ₂ O and SiO ₂ constituting the sodium silicate is preferably Na ₂ O: SiO ₂ = 1: 0.8 to 1: 4.

In the granular cleaning agent of the present invention, the particle size of the granular composition is preferably 0.5 to 6.8 mm.

In the granular detergent of the present invention, the granular composition is formed by granulating a raw material composition containing granular orthosilicate adsorbed with the liquid nonionic surfactant, the chelating agent, and the binder. It is desirable that it is a granular composition obtained by doing.

In the granular detergent of the present invention, the compounding ratio of the nonionic surfactant, the orthosilicate, the chelating agent, and the binder is 1: 4 to 6: 6 to 8: It is desirable that it is 1.5-3.5.

The method for producing a granular detergent according to the present invention comprises a raw material composition for preparing a raw material composition by mixing granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and a binder. A preparation process;
A granulating step for producing a granular composition by granulating the raw material composition;
A method for producing a granular detergent comprising a mixing step of mixing the granular composition and a chlorine agent,
A binder containing sodium silicate is used as the binder.

In the manufacturing method of the granular cleaning agent of this invention, it is desirable to granulate the said raw material composition to a particle size of 0.5-6.8 mm in the said granulation process.

The granular cleaning agent of the present invention is less likely to generate a powder of a granular composition, can be supplied by an automatic supply device, and can suppress decomposition due to contact between a nonionic surfactant and a chlorine agent.

(Granular detergent)
Hereinafter, the granular cleaning agent of the present invention will be described in detail.
The granular detergent of the present invention comprises a granular composition containing a granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent and a binder,
A granular cleaning agent comprising a chlorine agent,
The binder contains sodium silicate.

Examples of the liquid nonionic surfactant in the granular detergent of the present invention include polyoxyalkylene ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene dodecyl ether, polyoxyethylene myristyl (monotetradecyl). ) Ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene isostearyl ether, polyoxyethylene behenyl ether, polyoxyethylene octyl (2-ethyl-hexyl) ether, polyoxyethylene Alkyel ether, polyoxyethylene alkyl ether, narrow type polyoxyethylene alkyl ether, polyoxyethylene octyldecyl ether , Polyoxyethylene alkyl phenyl ether, polyoxyethylene (di) styrenated phenyl ether, polyoxyethylene β-naphthyl (naphthol) ether, polyoxyethylene hydrogenated castor oil ether, polyoxyethylene castor oil ether, polyoxyethylene lanolin Alcohol ether, polyoxyethylene phytosterol, polyethylene glycol monoalkyl fatty acid ester, polyethylene glycol dialkyl fatty acid ester, polyethylene glycol di-2-ethylhexoate, polyethylene glycol monoresin acid ester, polyethylene glycol monotol oil fatty acid ester, polyethylene Glycollanolin fatty acid ester, polyoxyethylene acetylenic glycol ether, polyoxyethylene Lenglycerin monoalkyl fatty acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, Polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan triisostearate, tetraoleic acid polyoxyethylene sorbitol, oxyethylene chain / oxypropylene chain block polymer, oxyethylene chain / oxypropylene chain block polymer, oxyethylene chain / Oxypropylene chain block polymer, oxyethylene chain / oxypropylene chain lander Polymer, oxypropylene chain / oxyethylene chain addition alkyl ether, oxyethylene chain / oxypropylene chain addition alkyl ether, ethylenediamine-polyoxypropylene chain / polyoxyethylene chain block, ethylenediamine-polyoxyethylene chain / polyoxypropylene chain block, Sorbitan ester, glyceride (glycerin (mono, di) fatty acid ester), polyglycerin alkyl fatty acid (mono, poly) ester, polyglycerin condensed ricinoleic acid ester, organic acid monoglyceride, propylene glycol fatty acid ester, sucrose fatty acid ester, alkyl glyceryl ether , Alkyl polyglucoside, lecithin and the like.
Of these, nonionic surfactants that are liquid in a temperature range of 10 to 40 ° C. may be used. In addition, 10-40 degreeC is a temperature range which can generally be taken in the granulation process demonstrated later.

The blending amount of the liquid nonionic surfactant contained in the granular composition is preferably 0.5 to 10% by weight.
If the blending amount of the liquid nonionic surfactant contained in the granular composition is less than 0.5% by weight, the blending amount of the liquid nonionic surfactant is too small and the detergency may decrease. If it exceeds 10% by weight, the amount of the liquid nonionic surfactant is too large, so that it exudes from the granular composition and adheres the granular composition to each other, and the fluidity of the granular cleaning agent is lowered. is there. Moreover, when a nonionic surfactant contacts a chlorine agent, a chlorine agent may be decomposed | disassembled.

Examples of the orthosilicate constituting the granular orthosilicate include an alkali metal salt of orthosilicate. Examples of the alkali metal salt of orthosilicate include sodium orthosilicate, potassium orthosilicate, lithium orthosilicate and the like.

The particle size of the granular orthosilicate may be, for example, 0.3 to 3.0 mm.
This is because the liquid nonionic surfactant can be adsorbed well, and the granular composition has excellent fluidity.
On the other hand, if the particle size of the granular orthosilicate is less than 0.3 mm, the particle size is too small and the liquid nonionic surfactant may be difficult to be adsorbed. If the particle size of the granular composition exceeds 3.0 mm, the particle size of the granular composition using the same may exceed 6.8 mm. If the particle size of the granular composition exceeds 6.8 mm, the particle size is too large. In other words, each component is difficult to disperse uniformly, and the fluidity of the granular composition (granular detergent) may be lowered.

In the present specification, the “particle size” of the particles is determined as follows.
First, the particles are passed through a sieve having a small mesh (for example, 0.5 mm).
Then, the particles remaining on the sieve are passed through a sieve having a large mesh (for example, 6.8 mm).
And about the particle | grains which passed the sieve, the particle size is described with the width | variety of "0.5-6.8 mm".

The amount of granular orthosilicate contained in the granular composition is preferably 20 to 50% by weight.
When the amount of the granular orthosilicate contained in the granular composition is less than 20% by weight, the liquid nonionic surfactant cannot be adsorbed so much. The detergency may be reduced. Moreover, when the compounding quantity of the granular orthosilicate contained in a granular composition exceeds 50 weight%, the compounding quantity of another component will decrease and detergency may fall.

Examples of chelating agents include aminodiamine-type chelating agents such as ethylenediaminetetraacetate and nitrilotriacetate, hydroxycarboxylic acids such as sodium citrate and sodium gluconate, sodium polyacrylate, acrylic acid / maleic acid copolymer, etc. Can be mentioned.

As for the compounding quantity of the chelating agent contained in a granular composition, it is desirable that it is 20 to 50 weight%.
If the blending amount of the chelating agent contained in the granular composition is less than 20% by weight, the chelating effect of the metal ions contained in the wash water may be low because the blending amount of the chelating agent is too small. Moreover, when the compounding quantity of the chelating agent contained in a granular composition exceeds 50 weight%, the compounding quantity of an alkaline component will decrease and detergency may fall.

The binder contains sodium silicate represented by the molecular formula Na ₂ O.nSiO ₂ .xH ₂ O.
n is preferably 0.8 to 4. That is, the molar ratio of Na ₂ O and SiO ₂ constituting sodium silicate is preferably Na ₂ O: SiO ₂ = 1: 0.8 to 1: 4. Moreover, n is more preferably 1, that is, sodium metasilicate.
Sodium metasilicate has a sufficiently high viscosity compared to sodium silicate with low silica content, such as sodium orthosilicate, so it is chelated with granular orthosilicate adsorbed with liquid nonionic surfactant. The agent can be bonded extremely firmly.
Therefore, the above-described operational effects of the present invention can be enjoyed more suitably.

The binder preferably contains sodium silicate hydrate or an aqueous sodium silicate solution.
When the binder contains sodium silicate hydrate or aqueous sodium silicate solution, the granular orthosilicate adsorbed with the liquid nonionic surfactant and the chelating agent are further added with sodium silicate. Since it can adhere | attach firmly, even if a granular composition and a chlorine agent contact each other and the surface of a granular composition is rubbed, the powder of a granular composition is hard to generate | occur | produce.
Examples of sodium silicate hydrate include sodium metasilicate pentahydrate and sodium metasilicate nonahydrate.
The concentration of the sodium silicate aqueous solution is preferably 6.0 to 50.0% by weight.

As the binder, potassium silicate may be used together with sodium silicate.
Even if potassium silicate is used, the effects of the present invention can be suitably enjoyed.

The blending amount of the binder containing sodium silicate is desirably 5.0 to 25% by weight.
When the amount of the binder containing sodium silicate is less than 5.0% by weight, the amount of the binder is too small, so the granular orthosilicate adsorbed with the liquid nonionic surfactant and the chelating agent are so strong. May not adhere. Moreover, since the compounding quantity of another component will decrease when the compounding quantity of the binder containing the sodium silicate contained in a granular composition exceeds 25 weight%, detergency may fall.

The particle size of the granular composition is preferably 0.5 to 6.8 mm.
When the particle size of the granular composition is 0.5 to 6.8 mm, the particle size has an appropriate particle size, and the contact between the chlorine agent and the nonionic surfactant is further reduced. And the decomposition of nonionic surfactants and the like can be suppressed more reliably. Therefore, the granular detergent containing such a granular composition can maintain better detergency over a longer period of time. In addition, each particle can be uniformly dispersed without the particle size of the granular composition being too large, and since the granular composition has good fluidity, poor supply of the granular detergent is unlikely to occur.
Moreover, since the granular composition will melt | dissolve in water as soon as the particle size of a granular composition is 6.8 mm or less, it can be used conveniently as a washing | cleaning agent.
On the other hand, when the particle size of the granular composition is less than 0.5 mm, the particle size is too small and contact between the chlorinating agent and the nonionic surfactant increases, and the chlorinating agent, nonionic surfactant, etc. May be easily decomposed. Moreover, it becomes easy for a granular composition to adhere to an apparatus.
Moreover, when the particle size of a granular composition exceeds 6.8 mm, a particle size is too large and it becomes difficult to disperse | distribute each component uniformly, and the fluidity | liquidity of a granular composition may become low.
Moreover, as for the particle size of a granular composition, it is more desirable that it is 0.8-5.6 mm. When the particle size of the granular composition is 0.8 to 5.6 mm, the contact between the chlorine agent and the nonionic surfactant is less likely to occur, and the fluidity of the granular composition becomes extremely high.
Moreover, the workability | operativity at the time of adjusting the particle size of a granular composition using a sieve is excellent in the particle size of a granular composition being 0.8 mm or more, and is excellent in mass-productivity.
Moreover, since a granular composition melt | dissolves in water more rapidly as the particle size of a granular composition is 5.6 mm or less, it can be used more suitably as a cleaning agent.
The particle size of the granular composition can be determined in the same manner as the particle size of the granular orthosilicate.

The granular composition is a granular composition obtained by granulating a raw material composition containing a granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and a binder. desirable.
In the granular composition obtained by granulation, the liquid nonionic surfactant is adsorbed on the granular orthosilicate. Further, it is considered that a chelating agent is coated on the surface of the granular orthosilicate by a binder containing sodium silicate.
Therefore, since the granular composition has good fluidity, poor supply of the granular detergent is unlikely to occur.
The granulation method will be described later in the description of the method for producing the granular detergent of the present invention.

The mixing ratio of the liquid nonionic surfactant, orthosilicate, chelating agent, and binder is 1: 4 to 6: 6 to 8: 1.5 to 3.5 by weight. Is desirable.
When the blending ratio of each component in the granular composition is the above weight ratio, each component is blended in a balanced manner, so that the granular orthosilicate adsorbed with the liquid nonionic surfactant and the chelating agent are added. It is possible to bond more firmly. Moreover, the granular cleaning agent containing such a granular composition is more excellent in detergency.

As for the compounding quantity of the granular composition in a granular detergent, it is desirable that it is 70-99.5 weight%.
When the blending amount of the granular composition in the granular detergent is 70 to 99.5% by weight, a high detergency can be exhibited.
On the other hand, if the amount of the granular composition in the granular detergent is less than 70% by weight, the detergency may decrease. If it exceeds 99.5% by weight, the amount of chlorine agent is too small and the bleaching effect is low. May be.
As for the compounding quantity of the granular composition contained in a granular cleaning agent, it is more desirable that it is 80-99.5 weight%, and it is still more desirable that it is 85-95 weight%.

In the granular detergent of the present invention, the granular composition may further contain a phosphate.
Phosphate is viscous by absorbing moisture relatively easily, so if phosphate is included in the granular composition, it will chelate with the granular orthosilicate adsorbed with the liquid nonionic surfactant. The agent adheres more firmly with the binder containing sodium silicate and the phosphate. Therefore, with such a granular detergent, the powder of the granular composition is less likely to be generated. Moreover, the granular cleaning agent containing the phosphate has higher detergency.

Examples of the phosphate include sodium tripolyphosphate, pyrophosphate, polyphosphate, and hexametaphosphate.

When phosphate is contained in the granular composition, the content of phosphate is preferably 20 to 50% by weight. This is because better detergency can be exhibited.
On the other hand, when the content of the phosphate contained in the granular composition is more than 50% by weight, the blending amounts of the nonionic surfactant, the chelating agent and the binder are reduced, and the detergency is reduced. Further, the amount of the binder is reduced, and the granular orthosilicate adsorbed with the liquid nonionic surfactant and the chelating agent do not adhere so strongly between the binder containing sodium silicate and the phosphate.
On the other hand, when the content of phosphate contained in the granular composition is less than 20% by weight, the content of phosphate is too small, and the effect of adding phosphate may not be sufficiently obtained.

In the granular detergent of the present invention, the granular composition may further contain a water-soluble polymer, sulfate, carbonate, and the like. It is desirable that at least one of these components is included.
Examples of water-soluble polymers include polyacrylates, salts of acrylic acid-maleic acid copolymers, salts of styrene-maleic acid copolymers, salts of ethylene-maleic acid copolymers, methyl vinyl ether-maleic acid Examples thereof include polymer carboxylates such as a salt of a copolymer.
Examples of the sulfate include anhydrous sodium sulfate, potassium sulfate, and anhydrous magnesium sulfate.

When the water-soluble polymer, sulfate, carbonate, etc. are contained in the granular composition, the blending amount of the water-soluble polymer mixed in the granular composition is 0.5 to 5% by weight of the whole granular composition. It is desirable that the blending amount of the sulfate is 1 to 15% by weight of the whole granular composition, and the blending amount of the carbonate is 0.5 to 5% by weight of the entire granular composition. It is desirable.

Examples of the chlorine agent contained in the granular cleaning agent of the present invention include calcium hypochlorite, sodium hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate, and the like.
The mixing ratio of the chlorine agent in the entire granular detergent is preferably 0.5 to 10% by weight. It is because the bleaching effect by a chlorine agent can fully be exhibited.
On the other hand, when the blending ratio of the chlorinating agent is less than 0.5% by weight, the chlorinating agent is too small and the bleaching effect may be lowered. Moreover, even if the compounding ratio of the chlorine agent exceeds 10% by weight, the bleaching effect is not improved so much.

In the granular cleaning agent of the present invention, the proportion of the effective chlorine amount after standing for 1 week in a constant temperature bath at 60 ° C. in the initial effective chlorine amount is preferably 70% or more, and more preferably 80% by weight or more. More preferred. When the chlorine stability is less than 70%, the nonionic surfactant and the chlorine agent may be decomposed to reduce the detergency.

(Production method of granular detergent)
Next, the manufacturing method of the granular cleaning agent of this invention is demonstrated.

The method for producing a granular detergent according to the present invention comprises a raw material composition for preparing a raw material composition by mixing granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and a binder. A preparation process;
A granulating step for producing a granular composition by granulating the raw material composition;
A method for producing a granular detergent comprising a mixing step of mixing the granular composition and a chlorine agent,
A binder containing sodium silicate is used as the binder.

(1) Raw material composition preparation step A predetermined amount of granular orthosilicate is weighed and charged into a mixer.
Next, a predetermined amount of a liquid nonionic surfactant is weighed, put into a mixer, and stirred for a predetermined time. Thereby, a liquid nonionic surfactant is made to adsorb | suck to a granular orthosilicate.
A predetermined amount of each of the chelating agent and the binder is weighed, put into this mixer, and mixed.
The raw material composition is prepared by the above operation.

(2) Granulation step The raw material composition prepared in step (1) is charged into a granulator, and granulated until the raw material composition has grown to a predetermined particle size, thereby preparing a granular composition.
By adjusting the granulation time, the rotational speed of the granulator, etc., the particle size of the granular composition can be adjusted to a desired range.

(3) Mixing step The granular composition produced in the step (2) and a predetermined amount of chlorinating agent are charged into a mixer and mixed uniformly at room temperature to produce the granular cleaning agent of the present invention.

In the step (1), a mixer is used, and in the step (2), a granulator is used. However, a granulator / mixer having both functions of a mixer and a granulator may be used in one apparatus. .
In this case, since the raw material composition produced by the mixer can be granulated as it is without being transferred to the granulator, it is advantageous in that the process can be omitted and the production cost can be reduced. .
Examples of the granulating mixer include a high speed mixer manufactured by Earth Technica, a Ladige mixer manufactured by Matsubo, and a Henschel mixer manufactured by Mitsui Mining.

Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.

Example 1
As a granular orthosilicate, 100 parts by weight of granular sodium orthosilicate (particle size: 0.5 to 2.0 mm) is weighed and put into a stirring granulator (high speed mixer, manufactured by Earth Technica Co., Ltd.). did.
As a liquid nonionic surfactant, 21 parts by weight of polyoxyalkylene monoalkyl ether (Pullrafac (registered trademark) LF900, manufactured by BASF Japan Ltd.) was weighed and put into a stirring granulator.
By operating the stirring granulator for about 3 minutes at 300 rpm, the liquid nonionic surfactant was adsorbed on the granular sodium orthosilicate.

As a chelating agent, 16 parts by weight of polyacrylic acid (Socharan (registered trademark) PA40 powder, manufactured by BASF Japan Ltd.) and 150 wt. And 48 parts by weight of sodium silicate aqueous solution (Na ₂ O: SiO ₂ = 1.75, concentration: 12.5% by weight, manufactured by Osaka Shoso Co., Ltd.) as a binder, and anhydrous sodium silicate (Aoshima) 50 parts by weight of Todake Sodium Silicate Co., Ltd.) was charged into the agitation granulator.

Then, the stirring granulator was operated for about 13 minutes under the condition of 100 rpm to produce a granular composition.

(Measurement of granulation rate)
The granulation rate was calculated about the produced granular composition.
In addition, the granulation rate in the Example of this specification and a comparative example is as a ratio (%) of the weight of the granular composition which has a particle size of 0.5-6.8 mm with respect to the total weight of the produced granular composition. Represent.
Specifically, it was calculated by the following method.
First, the produced granular composition was passed through a sieve having an aperture of 0.5 mm.
Subsequently, the granular composition remaining on the sieve was further passed through a sieve having an aperture of 6.8 mm.
The total weight (g) of the granular composition remaining on the sieve is divided by the total weight (g) of the granular composition before passing through a sieve having an opening of 0.5 mm, and multiplied by 100 to obtain a granulation rate (% ) Was calculated.
The granulation rate in this example was 90%.
That is, the granular composition prepared in Example 1 includes a granular composition having a particle size of 0.5 to 6.8 mm in a proportion of 90% by weight, and has a particle size of less than 0.5 mm or more than 6.8 mm. It contained a granular composition having a particle size in a proportion of 10% by weight.

950 parts by weight of the granular composition prepared in Example 1 and 50 parts by weight of a granular chlorinating agent (Neochlor 60G, manufactured by Shikoku Kasei Kogyo Co., Ltd.) are charged into a mixer, and about 10 at about 10 rpm at room temperature. The granular cleaning agent of the present Example was manufactured by mixing for a minute.

(Comparative Example 1)
A granular composition was produced in the same manner as in Example 1 except that water was used as a binder instead of the sodium silicate aqueous solution.
When the granulation rate of the granular composition was calculated in the same manner as in Example 1 using a sieve having an aperture of 0.5 mm and an sieve having an aperture of 6.8 mm, the granulation rate was 80%.
That is, the granular composition produced in Comparative Example 1 contains a granular composition having a particle size of 0.5 to 6.8 mm in a proportion of 80% by weight, and has a particle size of less than 0.5 mm or more than 6.8 mm. A granular composition having a particle size was contained in a proportion of 20% by weight.
Subsequently, mixing with a chlorine agent was performed in the same manner as in Example 1 to produce a granular cleaning agent.

(Comparative Example 2)
Materials used in the manufacture of the granular detergent used in Example 1, ie, granular sodium orthosilicate, polyoxyalkylene monoalkyl ether, polyacrylic acid, nitrilotriacetic acid trisodium, sodium polyacrylate, sodium silicate The aqueous solution, anhydrous sodium silicate, and the granular chlorine agent were all mixed in the blending amounts used in Example 1, and the stirring granulator was operated for about 13 minutes at 100 rpm to prepare a granular composition.
Since this granular composition is mixed with a chlorine agent, it can be regarded as a granular detergent.

When the granulation rate of the granular composition was calculated in the same manner as in Example 1 using a sieve having an aperture of 0.5 mm and an sieve having an aperture of 6.8 mm, the granulation rate was 85%.
That is, the granular composition produced in Comparative Example 2 contains a granular composition having a particle size of 0.5 to 6.8 mm in a proportion of 80% by weight, and has a particle size of less than 0.5 mm or exceeds 6.8 mm. It contained a granular composition having a particle size in a proportion of 15% by weight.

(Comparative Example 3)
A granular detergent was produced in the same manner as in Example 1 except that no sodium silicate aqueous solution as a binder was added.
Most of the composition taken out from the stirring granulator was powder, and was hardly granulated. In this case, it was judged that the granulated composition could not be produced.
In Comparative Example 3, since the granulated composition could not be produced, other characteristics were not evaluated.

(Evaluation of supply stability)
Using the granular detergents produced in Example 1 and Comparative Examples 1 and 2, the supply stability was evaluated as follows.

(I) Evaluation method A granular cleaning agent is put into a supply device A set in a constant temperature bath of 25 ° C. and a humidity of 70% and a supply device B set in a constant temperature bath of 35 ° C. and a humidity of 70%, respectively. did.
Thereafter, the supply devices A and B were operated intermittently while automatically controlling with the sensors for one month.
The supply stability of the granular detergent was evaluated as follows.
(Ii) Evaluation Criteria A: In any of the supply devices A and B, the granular cleaning agent was supplied smoothly without any solidification of the granular cleaning agent due to moisture.
○: In at least one of the supply devices A and B, solidification of the granular cleaning agent due to moisture on the carry-out gear and the inner wall surface was observed, but the granular cleaning agent was supplied smoothly.
As supply devices A and B, just set 1501 manufactured by Niitaka Corporation was used.

(Cleanability)
Under the following conditions, 7 glass cups as objects to be cleaned were washed using an automatic dishwasher (manufactured by Hoshizaki Electric Co., Ltd., WF-650UF).
After each glass cup after washing was dried, the appearance after washing was observed.
(I) Cleaning conditions Concentration of granular cleaning agent: 0.08% by weight
Total hardness of water: 50ppm
Object to be cleaned: A glass cup with a predetermined amount of dirt (egg, milk, oil mixture) applied to the inner wall and dried.
Washing conditions: Washing is performed for 60 seconds with 60 ° C washing water in which the granular detergent is dissolved, and then rinsing with 80 ° C rinse water for 15 seconds.
(Ii) Evaluation criteria A: No water spot is observed.
○: 2 to 3 water spots are seen.

(Chlorine stability)
(I) Measuring method Calculate the ratio of the effective chlorine amount contained in the granular detergent left in a constant temperature bath at 60 ° C for one week to the initial effective chlorine amount (effective chlorine amount before leaving for one week), and the calculation result Was evaluated according to the following criteria.
The amount of effective chlorine was measured as follows.
First, 1 g of granular detergent was collected, 0.2 g of potassium iodide was added, and 10 ml of glacial acetic acid was added.
Thereafter, the starch solution was titrated with an N / 10 sodium thiosulfate solution as an indicator, and the point at which the solution became colorless was taken as the end point.
And the effective chlorine concentration (%) as an effective chlorine amount was calculated by the following formula.
Effective chlorine concentration (%) = Titration amount (ml) × 0.3546 / weight of granular detergent (g)
(Ii) Evaluation criteria A: Ratio of effective chlorine quantity after one week to initial effective chlorine quantity is 95% or more X: Ratio of effective chlorine quantity after one week to initial effective chlorine quantity is less than 50%

Table 1 summarizes the binder type, granulation rate, supply stability, detergency, and chlorine stability in each example and comparative example.
In Comparative Example 2 in which a chlorine agent is mixed with other ingredients and granulated, the column of “chlorine agent” is indicated as “granulation blending”, and a granular composition is prepared by granulating components other than the chlorine agent. In other examples and comparative examples in which a chlorinating agent was mixed thereafter, the “chlorine agent” column was indicated as “separate blending”.

In Example 1, sodium silicate was used as the binder, and the granulation rate was as high as 90%. On the other hand, in Comparative Example 1 in which water was used as the binder, the granulation rate was as low as 80%, and in Comparative Example 3 in which no binder was used, a granulated composition could not be produced.

In Example 1, the supply stability was good, and solidification of the granular composition in the supply apparatus was not recognized. The reason is that because the granulation rate is high, the proportion of powder with a small particle size is low, and sodium silicate as a binder covers the periphery of the granular orthosilicate and chelating agent to make it vitreous. In order to form a film having similar properties, even if a powder having a small particle size is present, it is difficult to adhere to the wall surface of the automatic feeder.

On the other hand, in Comparative Example 1, the supply stability was inferior, and solidification of the granular composition in the supply apparatus was observed. The reason is that since the granulation rate is lower than that of Example 1, the ratio of the powder having a small particle size is high, and the powder having the small particle size is likely to adhere to the wall surface of the automatic supply device. Can be mentioned.

In Example 1, since the chlorine agent was blended separately from the granular composition, decomposition due to contact between the nonionic surfactant and the chlorine agent was prevented, and the chlorine stability was excellent.
Since the chlorine stability is excellent, the detergency was also high.
On the other hand, in Comparative Example 2, since the granulation was performed by mixing the chlorine agent and the nonionic surfactant, the decomposition due to the contact between the nonionic surfactant and the chlorine agent occurred and the chlorine stability was poor.
In addition, the cleanability was low due to poor chlorine stability.

Claims (6)

A granular composition comprising a granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent and a binder;
A granular cleaning agent comprising a chlorine agent,
The binder contains sodium silicate hydrate or sodium silicate aqueous solution ,
The molar ratio of Na ₂ O and SiO ₂ constituting the sodium silicate hydrate or sodium silicate aqueous solution is Na ₂ O: SiO ₂ = 1: 0.8 to 1: 4. Granular cleaning agent. The granular cleaning agent according to claim 1 , wherein the granular composition has a particle size of 0.5 to 6.8 mm. The granular composition is obtained by granulating a raw material composition containing granular orthosilicate adsorbed with the liquid nonionic surfactant, the chelating agent, and the binder. The granular cleaning agent according to claim 1 or 2 . The compounding ratio of the nonionic surfactant, the orthosilicate, the chelating agent, and the binder is 1: 4-6: 6-8: 1.5-3.5 by weight. The granular cleaning agent according to any one of claims 1 to 3 . A raw material composition preparation step of preparing a raw material composition by mixing a granular orthosilicate adsorbed with a liquid nonionic surfactant, a chelating agent, and a binder;
A granulating step for producing a granular composition by granulating the raw material composition;
A method for producing a granular detergent comprising a mixing step of mixing the granular composition and a chlorine agent,
As the binder, using a binder containing sodium silicate hydrate or aqueous sodium silicate solution ,
The molar ratio of Na ₂ O and SiO ₂ constituting the sodium silicate hydrate or sodium silicate aqueous solution is Na ₂ O: SiO ₂ = 1: 0.8 to 1: 4. Manufacturing method of granular detergent. The manufacturing method of the granular cleaning agent of Claim 5 which granulates the said raw material composition to a particle size of 0.5-6.8 mm in the said granulation process.