CN1119407C - Method for producing nonionic detergent granules - Google Patents

Abstract

Provided is a method for producing nonionic detergent granules that use a nonionic active agent as a main base, have a high bulk density, have excellent powder flow properties and non-caking properties, and suppress blocking. A method for producing nonionic detergent granules with a bulk density of 0.6 to 1.2 g/ml using the following steps: step (1): preparing an aqueous solution containing (a) an alkaline agent, (b) a nonionic active agent and/or , (c) the process of selecting the acid precursor of the lamellar-oriented anionic surfactant and (d) the mixture of the water-soluble nonionic organic compound, and adding the (c) component into the mixer to prepare the mixture according to a specific form Step, step (2): is a step of preparing granules by rotating the mixture obtained in step (1) with a stirrer at a temperature above the temperature at which the acid precursor can be neutralized, and granulating while increasing the bulk density.

Description

Process for the manufacture of nonionic detergent granules

The present invention relates to a process for the manufacture of nonionic detergent granules. More specifically, it relates to non-ionic activity that has a high degree of freedom in formulating composition, high bulk density, excellent powder flow characteristics, good non-caking properties during long-term storage, no bleeding of liquid components, and suppresses blocking The invention discloses a method for making nonionic detergent granules in which the agent is used as the main base.

Most nonionic active agents are liquid substances at room temperature, and when a powder detergent is blended in a large amount in a liquid state as it is, the nonionic active agent tends to slowly ooze out over time. Owing to such seepage, seeping into the inner surface of the paper container causes caking, and there is a problem that the detergent is solidified.

In GB2294056A communiqué, the manufacture method of nonionic detergent granules has been disclosed, the method is to mix alkaline builder in the acid precursor of nonionic active agent and anionic surfactant capable of selecting lamellar orientation, by Neutralize the above-mentioned acid precursor to form a gelled product containing a nonionic active agent, add the gelled product to a binder, and use a stirring mixer to rotate the mixture of detergent raw materials while granulating to obtain a nonionic Detergent granules. Such nonionic detergent granules are resistant to run-off and caking. However, even such detergent granules, under low temperature and compacted state, tend to cause adhesion phenomenon (detergent granules are attached to each other slightly under the dead weight of the granules) in the case of storage and transportation. Phenomenon). Such a sticking phenomenon may become a main factor that damages the usability of the consumer and the image of the product.

In addition, there is more room for discussion about the stability of detergent granules during long-term storage of detergent granules.

Therefore, the object of the present invention is to provide a method for producing nonionic detergent granules that use a nonionic active agent as a main base, have a high bulk density, have excellent fluidity and non-caking properties of the powder, and suppress blocking.

The present inventors conducted in-depth research and found that, in nonionic active agents and/or nonionic active agent aqueous solutions, water-soluble nonionic organic compounds with a melting point of 45° C. The acid precursor of the anionic surfactant is blended with an alkaline builder and an alkaline agent that is a porous oil-absorbing carrier, and by neutralizing the acid precursor, a gelled product containing a nonionic active agent is formed. Add a binder to the chemical compound, use a stirring mixer to rotate the mixture of detergent raw materials, and granulate while increasing the density, improve the long-term storage stability of the obtained nonionic detergent granules, and suppress the blocking property, thereby completing the invention.

That is, the gist of the present invention is about:

[1] A method for producing nonionic detergent granules characterized by obtaining nonionic detergent granules having a bulk density of 0.6 to 1.2 g/ml using the following steps,

Step (1): preparation contains (a) alkaline builder and/or alkaline porous oil-absorbing carrier, (b) nonionic active agent and/or nonionic active agent aqueous solution, (c) energy The process of selecting the acid precursor of the lamellar-oriented anionic surfactant, and (d) a mixture of a water-soluble nonionic organic compound having a melting point of 45° C. or higher and an average molecular weight of 1,000 or higher, that is,

(i) pre-mixing ingredients (b) and (c) and adding them to a mixer,

(ii) a form in which the ingredients (b) and (c) are added to the mixer one by one at the same time, and

(iii) A form in which component (c) is added to the mixer after the addition of component (b) to the mixer starts or after addition is completed, and component (c) is added to the mixer in any form selected from the group consisting of the above forms The process of preparing the mixture in the machine, and

Step (2): At a temperature above the temperature at which the acid precursor can be neutralized, the mixture obtained in the step (1) is rotated using an agitator mixer, and granulated while increasing the bulk density to prepare granules.

[2] The production method described in the above [1], wherein the component (c) is a saturated or unsaturated fatty acid with 10 to 22 carbon atoms, an alkyl sulfuric acid with 10 to 22 carbon atoms, or a fatty acid with 10 to 22 carbon atoms. Selected from the group consisting of α-sulfonated fatty acid and polyoxyethylene alkyl ether sulfuric acid with 10 to 22 carbon atoms (however, the average number of added moles of ethylene oxide is 0.2 to 2.0),

[3] The production method described in the above [1] or [2], wherein the compounding amount of the component (c) is 5 to 100 parts by weight based on 100 parts by weight of the component (b),

[4] The production method described in any one of the above [1] to [3], wherein the basic porous oil-absorbing carrier is a 1 g/l 20°C aqueous solution or a dispersion that exhibits a pH of 8 or higher, according to The pore volume of the mercury intrusion method is 100-600cm ³ /100g, the specific surface area according to the BET method is 20-700m ² /g, the oil absorption according to JIS K 5101 is 100ml/100g or more, and the average particle size or primary particle Porous oil-absorbing carrier with an average particle size of 10 μm or less,

[5] The production method described in any one of the above-mentioned [1]-[4], in the step (1), a neutral or acidic builder and/or spray-dried granules are further blended,

[6] is the production method described in any one of the above-mentioned [1] to [5], wherein the compounding amount of the detergent raw material in the step (1) is selected according to the following (A) or (B),

(A) The total compounding amount of (b) component, (c) component and (d) component is 10 to 60 parts by weight, (a) component is 40 to 90 parts by weight, and a neutral or acidic auxiliary The lotion is 0-10 parts by weight,

(B) The total compounding amount of (b) component, (c) component, and (d) component is 10 to 60 parts by weight, (a) component is 10 to 80 parts by weight, and is a neutral or acidic builder The agent is 0 to 10 parts by weight, and the spray-dried particles are 10 to 80 parts by weight,

[7] The production method described in any one of the above-mentioned [1] to [6], wherein the step (2) is performed at the temperature indicated in the following (A), (B) or (C),

(A) When the mixed solution obtained by mixing (b) component, (c) component and (d) component is used to carry out step (1), the melting temperature of the mixed solution,

(B) When step (1) is carried out using a mixed solution composed of any two components of the three components (b), (c) and (d) and the remaining components, the mixed solution The higher temperature of the melting temperature or the melting point of the residual ingredient,

(C) When step (1) is performed by adding (b) component, (c) component, and (d) component one by one, the melting point of these compounds is the highest,

[8] is the production method described in any one of the above-mentioned [1]-[7], wherein the melting point of the component (d) is 45-100°C, and the average molecular weight is 1000-30000,

[9] is the production method described in the above [8], wherein the component (d) is a polyether-based nonionic organic compound,

[10] is the production method described in the above [8], the component (d) is a polyoxyethylene type nonionic organic compound,

[11] The production method according to any one of the above [1] to [10], wherein the nonionic detergent granules obtained have a blocking property of 20% of the container remaining rate.

Hereinafter, the present invention will be described in detail.

About the process (1)

Step (1) is to prepare (a) alkaline builder and/or alkaline porous oil-absorbing carrier, (b) nonionic active agent and/or nonionic active agent aqueous solution, (c) optional The step of (d) a mixture of an acid precursor of an anionic surfactant having a lamellar orientation and (d) a water-soluble nonionic organic compound having a melting point of 45° C. or higher and an average molecular weight of 1,000 or higher, that is,

(i) pre-mixing ingredients (b) and (c) and adding them to a mixer,

(ii) a form in which the ingredients (b) and (c) are added to the mixer one by one at the same time, and

(iii) A form in which component (c) is added to the mixer after the addition of component (b) to the mixer starts or after addition is completed, and component (c) is added to the mixer in any form selected from the group consisting of the above forms The process of preparing the mixture in the machine.

As (a) component, the builder which is basic and/or the porous oil-absorbing carrier which is basic is used. Here, as an alkaline builder, one or more organic or inorganic powder builders having a pH of 8 or higher as a 1 g/l 20° C. aqueous solution or dispersion liquid can be preferably used.

Alkaline organic builders, preferably citrate, polyacrylate, acrylic acid-maleic acid copolymer salt, polyglyoxylate. In particular, sodium citrate, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, and sodium polyglyoxylate having an average particle diameter of 500 μm or less are preferable. These may be used individually or in mixture of 2 or more types. The measurement of the average particle diameter, when the average particle diameter of the builder is 100 μm or more, is measured using a standard sieve of JIS Z 8801 after shaking for 5 minutes, and then measured from the weight fraction based on the size of the sieve. Moreover, when it is less than 100 micrometers, the average particle diameter can be measured using the method of light scattering, for example, using the microparticle measuring device (made by Horiba Seisakusho Co., Ltd.).

Next, as alkaline inorganic builders, carbonates, bicarbonates, sulfites, silicates, tripolyphosphates, other phosphates, crystalline aluminosilicates, amorphous Aluminosilicate etc. Specifically, alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate (JIS No. 1 or No. 2 sodium silicate, etc.), have an ion exchange rate of 100CaCO ₃ mg/g or more. Capability of crystalline silicate compounds, orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate and other phosphates (alkali metal salts of sodium, potassium, etc.) and crystalline , Amorphous sodium aluminosilicate.

Among these alkaline inorganic powder builders are sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium sulfite, crystalline sodium aluminosilicate and crystalline silicate with an ion exchange capacity of 100CaCO ₃ mg/g or more One or more compounds selected from the compound group preferably have an average particle diameter of 500 μm or less, more preferably 350 μm or less. The average particle diameter of an inorganic powder builder can be measured by the same measuring method as the average particle diameter of the above-mentioned organic powder builder. Moreover, these organic builders and inorganic builders can also be mixed and used.

As an alkaline porous oil-absorbing carrier, for example, a 1 g/l aqueous solution or dispersion at 20°C can be preferably used if the pH is 8 or higher, and the pore volume according to the mercury porosimetry is 100 to 600 cm ³ /100 g, according to BET. A porous oil-absorbing carrier with a specific surface area of 20 to ^700m2 /g, an oil absorption of 100ml/100g or more, preferably 150ml/100g or more according to JIS K 5101, and an average particle diameter or primary particle average particle diameter of 10μm or less. The average particle diameter can be measured by the same method as in the case of the above-mentioned builder. Preferable examples of such a porous oil-absorbing carrier include the following.

1) Amorphous aluminosilicate

Amorphous aluminosilicates containing amorphous aluminosilicates as main components include Aluminum Silicate P820 manufactured by Tegusa Corporation, TIXOLEX 25 manufactured by Han Im Chemical Co., Ltd., and those represented by the following general formula can be preferably used. And they have a feature called having ion exchange capacity.

①x(M ₂ O)·Al ₂ O ₃ ·y(SiO ₂ )·w(H ₂ O) (M in the formula represents alkali metal atoms such as sodium and potassium, and x, y and w represent values within the following range The number of moles of each component of .

0.2≤x≤2.0

0.5≤y≤10.0

w is any integer including 0)

②x(MeO)·y(M ₂ O)·Al ₂ O ₃ ·z(SiO ₂ )·W(H ₂ O) (Me in the formula represents alkaline earth metal atoms such as calcium and magnesium, and M represents alkali such as sodium and potassium Metal atoms, x, y, Z, and w represent the number of moles of each component within the following numerical ranges.

0.001≤x≤0.1

0.2≤y≤2.0

0.5≤z≤10.0

w is any integer including 0)

2) Calcium silicate

Flu-lite R manufactured by Tokuyama Soda Co., Ltd., Hubersorb ^R 600 manufactured by Hiyuba Corporation, and the like are exemplified.

Amorphous aluminosilicates and calcium silicates may be used alone or in combination. Among these porous oil-absorbing carriers, amorphous aluminosilicates with a water content of 15 to 30% by weight are particularly preferred because they are rich in neutralization reactions with fatty acids. In addition, the average particle diameter of the primary particles is preferably 0.1 μm or less, and the average particle diameter of the aggregates is preferably 50 μm or less. The water content mentioned here is calculated from the weight of the sample after heat treatment at 800° C. for 1 hour and before heat treatment.

The (b) component is a nonionic active agent and/or an aqueous solution of a nonionic active agent.

The nonionic active agent used in the present invention is not particularly limited, and commonly used known nonionic active agents can be used. Among them, suitable is, for example, liquid or slurry at 40° C., HLB in the range of 9.0 to 16.0, low contamination, and good foaming and defoaming. The HLB referred to here is defined by the following documents. That is, it is calculated according to the definition of W.C.Griffin in Kirk-Othmer Encyclopedia of Chemical Technology 3rd ed. (M.Grayson ed.) vol8 Weily Interscience, New York1979 pp900-930.

As a specific example of nonionic active agent, the main nonionic active agent is expected to use polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, 1020 carbon atoms, preferably 10 to 15 carbon atoms, more preferably 12 to 14 A polyoxyethylene alkyl ether having an average addition mole number of ethylene oxide of 5 to 15, preferably 6 to 12, more preferably 6 to 10 carbon-atom linear and branched primary and secondary alcohols. In addition, the polyoxyethylene alkyl ether generally contains a large amount of alkyl ether having a low addition mole number of ethylene oxide, but it is desirable to use a 0 to 3 mole addition product of 35% by weight or less, preferably 25% by weight or less.

Others, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether carboxylate alkyl ester, polyoxyethylene polyoxy Propylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher alkanolamine, alkyl glycoside, alkyl amine oxide, etc.

The above-mentioned nonionic active agent may be blended in a liquid state at room temperature, or may be blended in an aqueous solution (that is, an aqueous solution of a nonionic active agent). Alternatively, the two can also be mixed. Since it is used in an aqueous solution state, it has the effect of accelerating the neutralization reaction of the acid precursor of the alkaline builder and/or the alkaline porous oil-absorbing carrier and the anionic surfactant capable of selecting lamellar orientation. As the nonionic active agent used when blending as an aqueous solution, the same ones as above can also be used. That is, suitable as the nonionic active agent aqueous solution is 10～20 carbon atoms, more preferably 10～15 carbon atoms, most preferably 12～14 carbon atoms the average addition of ethylene oxide of linear and branched primary and secondary alcohols An aqueous solution of polyoxyethylene alkyl ether with a mole number of 5-15, more preferably 6-12, most preferably 6-10.

The water content of the nonionic active agent aqueous solution is preferably at most 15% by weight, more preferably at most 10% by weight, most preferably at most 8% by weight. From the viewpoint of suppressing liquid crystallization and high viscosity of the mixture, the water content is preferably 15% by weight or less.

The acid precursor of the anionic surfactant which can select the lamellar orientation of (c) is, for example, the acid precursor of the anionic surfactant which has the following (i) or (ii) property.

(i) Mixing with a nonionic active agent and/or an aqueous solution of a nonionic active agent, and neutralizing the resulting mixture with sodium carbonate, an acid precursor of an anionic surfactant showing anisotropy when observed with a polarizing microscope.

The confirmation method of anisotropy is described below. Above the melting point of the acid precursor of the anionic surfactant used in the confirmation, use a high-speed shear mixer (homogenizer) to mix 80 parts by weight of the nonionic active agent, 20 parts by weight of the acid precursor, and the acid precursor Sodium carbonate powder (average particle size about 5 μm) was mixed thoroughly and neutralized. A part of the mixture was heated up to the melting point of the acid precursor, cooled, maintained at 40° C., and observed with a polarizing microscope (manufactured by Nikon, OPTIPHOT-POL).

(ii) mixed with a nonionic active agent and/or an aqueous solution of a nonionic active agent, neutralizing the resulting mixture with sodium carbonate, an acid precursor of an anionic surfactant showing a lamellar orientation peak when analyzed by X-ray diffraction .

The measurement method is described below. Using the Rigaku RAD system (X-ray source Cu (Kα: λ = 1.5405), measurement range: 2θ = 2° to 30°) to measure the surface activity of the sample [(nonionic active agent and/or nonionic active agent aqueous solution)/anionic surface activity The acid precursor of agent=80/20～20/80 (weight ratio)].

The acid precursors of the anionic surfactants that can be selectively oriented used in the present invention are not particularly limited, for example, saturated or unsaturated fatty acids with 10 to 22 carbon atoms, preferably saturated or unsaturated fatty acids with 12 to 18 carbon atoms Unsaturated fatty acid, alkyl sulfuric acid of 10-22 carbon atoms, preferably alkyl sulfuric acid of 12-14 carbon atoms, α-sulfonated fatty acid of 10-22 carbon atoms, preferably of 14-16 carbon atoms α-sulfonated fatty acid, and polyoxyethylene alkyl ether sulfuric acid with 10 to 22 carbon atoms and 0.2 to 2.0 average added moles of ethylene oxide, preferably 12 to 14 carbon atoms and average added moles of ethylene oxide 0.5-1.5 polyoxyethylene alkyl ether sulfuric acid, etc. The number of carbon atoms of the above compound is preferably 10 or more from the viewpoint of detergency and odor, and preferably 22 or less from the viewpoint of detergency and solvent property.

As the above-mentioned acid precursor used in the present invention, fatty acids are preferred, and specifically, saturated acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and unsaturated acids such as oleic acid can be mentioned. A mixture of more than one selected from the group consisting of saturated acids. In particular, saturated acids such as myristic acid (Lunuck MY-98, manufactured by Kao Corporation, etc.) and palmitic acid (Lunatsuk P-95, manufactured by Kao Corporation, etc.) are preferably used.

In addition, the compounding amount of the acid precursor of the anionic surfactant capable of selectively aligning is not particularly limited, but it is preferably 5 to 100 parts by weight relative to 100 parts by weight of the nonionic active agent and/or the aqueous solution of the nonionic active agent number, more preferably 10 to 60 parts by weight, particularly preferably 15 to 50 parts by weight. The compounding amount of the acid precursor is preferably 5 parts by weight or more from the viewpoint of forming a gelled product, and preferably not more than 100 parts by weight from the viewpoint of suppressing solvent resistance.

The component (d) is a water-soluble nonionic organic compound having a melting point of 45° C. or higher and an average molecular weight of 1,000 or higher. By using the component (d), bleeding of the nonionic active agent during long-term storage of the nonionic detergent granules obtained as granules can be prevented, and non-blocking and non-caking properties can be improved. As (d) component, a melting point of 45 to 100° C. and a water-soluble nonionic organic compound with an average molecular weight of 1,000 to 30,000 are more suitable. As such an organic compound, a polyether type nonionic organic compound and a polyoxyethylene type nonionic organic compound are mentioned. Specifically, polyethylene glycol (PEG), polypropylene glycol, polyoxyethylene alkyl ether, pluronic type nonionic active agent, etc. are mentioned. Among them, PEG is the best from the viewpoint of the physical properties of the obtained granulated product. As PEG, the average molecular weight is preferably 3,000 to 30,000, and most preferably 4,000 to 15,000.

Moreover, in a process (1), you may further mix|blend a neutral or acidic builder and/or spray-dried granule. Thereby, the effect of further improving solubility and detergency can be expected. In addition, the purpose of using spray particles is to ① suppress the bulk density, and ② increase the oil absorption of the builder.

Examples of the above-mentioned neutral or acidic builders include organic or inorganic powder builders that exhibit a pH of 8 or less as a 1 g/l 20° C. aqueous solution or dispersion liquid.

Specifically, from Glauber's salt, sodium chloride, citric acid, polyacrylic acid or its partial neutralization, acrylic acid-maleic acid copolymer acid or its partial neutralization, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone 1 or more compounds selected from the group consisting of non-dissociative polymers such as carboxymethyl cellulose and cold water soluble urethane polyvinyl alcohol. As for their particle diameters, the average particle diameter is preferably at most 500 μm, particularly preferably at most 350 μm. Among them, one or more compounds selected from the group consisting of Glauber's salt, citric acid, polyacrylic acid or a partially neutralized product thereof, and acid of an acrylic acid-maleic acid copolymer or a partially neutralized product thereof are particularly preferable.

As the spray-dried granules, for example, granules obtained by spray-drying an aqueous slurry containing one or more organic or inorganic builders described above according to a known method can be used. Among the above-mentioned builders, those selected from tripolyphosphate, carbonate, crystalline or non-crystalline aluminosilicate, citrate, Glauber’s salt, sulfite, polyacrylate, acrylic acid-maleic acid copolymer Salt, polyglyoxylate, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, cold water soluble urethane polyvinyl alcohol and other non-dissociative polymers, anionic active agents, non- More preferably, one or more compounds selected from the group consisting of an ionic active agent and a fluorescent dye. In particular, carbonates such as sodium carbonate, crystalline aluminosilicates, citrates, mirabilite, sulfites such as sodium sulfite, polyacrylates such as sodium polyacrylate, sodium salts of acrylic acid-maleic acid copolymers, etc. One or more compounds selected from the group consisting of salts of acrylic acid-maleic acid copolymers, polyglyoxylates such as sodium polyglyoxylate, anionic active agents, nonionic active agents, and fluorescent dyes are preferred. Furthermore, the average particle diameter of the sprayed particles is preferably from 100 to 600 μm, particularly preferably from 150 to 400 μm.

In addition, the water content of the aqueous slurry is preferably from 30 to 80% by weight, more preferably from 35 to 60% by weight. In the manufacture of the spray-dried granules, if necessary, one or more anionic, cationic or nonionic active agents may be added to account for 5% by weight or less in the spray-dried granules. other additions.

The compounding amount of the detergent raw material in the step (1) is not particularly limited, but by setting as shown in the following (A) or (B), it is possible to suitably prepare a nonionic active agent as the main base agent. A mixture of detergent raw materials.

(A) The total amount of component (b), component (c) and component (d) is preferably from 10 to 60 parts by weight, more preferably from 15 to 50 parts by weight, particularly preferably from 20 to 40 parts by weight Parts; (a) component is preferably 40 to 90 parts by weight, more preferably 50 to 85 parts by weight, especially preferably 60 to 80 parts by weight; and a neutral or acidic builder is better It is 0 to 10 parts by weight, preferably 0 to 5 parts by weight.

(B) The total amount of component (b), component (c) and component (d) is preferably from 10 to 60 parts by weight, more preferably from 15 to 50 parts by weight, particularly preferably from 20 to 40 parts by weight Parts; (a) component is preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, particularly preferably 20 to 60 parts by weight; neutral or acidic builder is preferably 0 to 10 parts by weight, preferably 0 to 5 parts by weight; and the spray-dried particles are preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, especially preferably 20 to 60 parts by weight number of copies.

The mixing method of step (1) is not particularly limited, but component (c) and component (a) are not mixed before component (b), specifically, for example (i) component (b) and component (c) are mixed in advance , and then added to the mixer, (ii) the (b) component and (c) component are added to the mixer one by one at the same time, and (iii) after the addition of (b) component to the mixer starts or after adding After the completion, the form of adding the (c) component to the mixer, according to any form selected from the group consisting of the above-mentioned forms, adding the (c) component to the mixer to prepare the mixture is suitable because it promotes the formation of the gel of. That is, in order to form a gelled substance, it is preferable to carry out neutralization reaction of (a) component and (c) component in presence of (b) component. Therefore, the neutralization reaction of (a) component and (c) component in the absence of (b) component exists in the tendency which suppresses formation of a gelled substance, and it is unsuitable.

When preparing the mixture in a batch manner, various methods such as the following (A) to (C) can be employed, for example.

(A) A method of preparing [mixture of (b) component, (c) component, and (d) component] in advance, and then mixing with (a) component. At this time, it is more appropriate that the temperature of the mixture is equal to or higher than the melting temperature of the above-mentioned liquid mixture. More specifically, the following forms are mentioned, for example.

1) First, put (a) component in the mixer, and then mix [mixture of (b) component, (c) component, and (d) component].

2) A form in which component (a) and [mixed solution of component (b), component (c) and component (d)] are simultaneously loaded into the mixer.

Among the above, the method of 1) is suitable from the viewpoint of promoting the formation of a gelled product.

(B) From the three components (b), (c) and (d) components, prepare a mixed solution in which any two components are combined in advance, and then mix the mixed solution, the remaining component, and the (a) component , the method of modulating the mixture. At this time, the temperature of the mixture is more suitably higher than the melting temperature of the liquid mixture or the melting point of the remaining components, whichever is higher. More specifically, the following forms are mentioned, for example.

1) Put (a) component in the mixer first, mix [mixture of (b) component and (d) component], and then mix (c) component.

2) After putting the (a) component into the mixer first, [the mixture of (b) and (d) components] and (c) component are respectively simultaneously charged.

3) After putting (a) component in the mixer first, mix (b) component, and then mix [a mixture of (c) component and (d) component].

4) After putting the (a) component into the mixer, the (b) component and [the mixture of (c) and (d) components] are simultaneously charged.

5) After putting (a) component in the mixer first, mix (d) component, and then simultaneously mix [a mixture of (b) component and (c) component].

6) After putting the (a) component into the mixer first, the (d) component and [the mixture of (b) and (c) components] are simultaneously charged.

7) Put the (a) component in the mixer first, mix [the mixture of (b) component and (c) component], and then mix the form of (d) component.

C) The method of mixing (b) component, (c) component, and (d) component with (a) component individually. At this time, it is more appropriate that the temperature of the mixture is not less than the highest melting point among the melting points of these compounds. More specifically, the following forms are mentioned, for example.

1) After putting (a) component in the mixer first, mix (b) component, then mix (d) component, and then mix the form of (c) component.

2) After putting (a) component in the mixer first, mix (b) component, and then charge (c) and (d) components at the same time.

3) After putting (a) component in the mixer first, mix (b) component and (d) component simultaneously, and then mix (c) the form of component.

4) A form in which (b) component, (c) component, and (d) component are simultaneously mixed after putting (a) component in the mixer.

5) After putting (a) component in the mixer first, mix (b) component and (c) component at the same time, and then mix the form of (d) component.

About mixers and mixers for preparing a mixed solution consisting of any two components from three components (b), component (c) and component (d), or a mixed solution consisting of these three components The method is not particularly limited, and may be a general mixer and a mixing method.

In addition, in the case of carrying out the present invention in a continuous manner, firstly, the detergent raw materials are mixed continuously or mixed and granulated simultaneously, but before the component (b), the components (c) and (a) are not mixed. The ingredients are preferred, and the method of supplying other detergent raw materials is not particularly limited. For example, the following various methods can be selected.

1) A method of continuously supplying [mixture of (b) component, (c) component, and (d) component] and (a) component.

2) A method of continuously supplying [mixture of component (b) and component (c)], component (a) and component (d).

3) A method of continuously supplying [mixture of (b) component and (d) component], (a) component, and (c) component.

4) A method of continuously supplying [mixture of (c) component and (d) component], (a) component, and (b) component.

5) A method of continuously supplying (a) component, (b) component, (c) component, and (d) component.

In addition, when the present invention continuously carries out the granulation of nonionic detergent particles, as another embodiment, (a) component, (b) component, (c) component and (d) The ingredients are all mixed, and the mixture is then continuously fed to the granulation process. In addition, it is preferable to spray and supply the liquid components in any of the batch-type and continuous-type methods.

In addition, in the present invention, there are no particular limitations on the supply system of the neutral or acidic builder and the spray-dried granules, whether it is a batch type or a continuous type.

Furthermore, the temperature at the time of mixing in the step (1) is preferably the above-mentioned temperature condition, and mixing can be performed at a temperature above the temperature at which the acid precursor of the anionic surfactant capable of selecting lamellar orientation can be neutralized. In this case, it is preferable from the viewpoint of productivity to perform step (2) simultaneously with step (1) to shorten the mixing and granulation time. Accordingly, such methods are also within the scope of the present invention.

In this way, in order to set the temperature of the mixture at a desired temperature in the step (1), for example, the temperature of the warm water can be appropriately adjusted using a mixer provided with a water jacket capable of flowing a liquid such as warm water.

As an apparatus suitable for use in the process (1) of this invention, the following apparatus is mentioned. In the case of batch operation, the devices (1) to (4) are preferred.

(1) It is a mixer that has a stirring shaft inside a mixing tank, and a stirring blade is mounted on the stirring shaft, and performs powder mixing. For example, there are Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.), high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Pauretsuku Co., Ltd.), and the most suitable one is a horizontal granulator. In the type mixing tank, there is a stirring shaft in the center of the cylinder, and stirring blades are installed on the stirring shaft to carry out powder mixing. For example, there are Redeige mixer (manufactured by Matsuzaka Technology Research Co., Ltd.), Prosia mixer (Pacific Machine Co., Ltd. Work (strain) manufacturing).

(2) A mixer that performs mixing by rotating a V-shaped mixing tank, for example, a V-shaped mixer (manufactured by Fuji Power Co., Ltd.).

(3) A mixer that performs mixing by rotating a helical blade that forms a helix in a semi-cylindrical fixed container, for example, a screw mixer (manufactured by Fuji Power Co., Ltd.).

(4) Along the conical container, the screw is centered on the axis parallel to the wall of the container, and revolves while rotating on its own axis to perform mixing. For example, there are Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), SV mixer (manufactured by Kobelco Pantech Co., Ltd.).

As an apparatus for continuous operation, apparatuses of the following (1) to (3) are suitably used.

(1) A continuous mixer with a vertical cylinder equipped with a powder inlet and a main rotating shaft equipped with mixing blades, the main rotating shaft is supported by a bearing on the upper part, and the discharge side is opened, such as Frekisomix Type (manufactured by Powreik).

(2) A continuous mixer in which raw materials are put into the top of a circular plate with a stirring pivot, the circular plate is rotated at a high speed, and mixed by shearing action, such as a jet mixer (manufactured by Fenken Pantex), a screw Mixer (manufactured by Pacific Machinery Co., Ltd.).

(3) A continuous mixer that has a stirring shaft inside a mixing tank, a stirring blade is attached to the stirring shaft, and performs powder mixing. For example, there is a Henschel mixer (manufactured by Mitsui Miike Chemical Equipment Co., Ltd.). Furthermore, a device such as a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powrec Co., Ltd.) can also be used as a continuous apparatus. It is preferable to have a stirring shaft in the center of the cylinder in a horizontal mixing tank, and a stirring blade is installed on the stirring shaft to carry out a continuous mixer in the form of powder mixing. , Procia Mixer (manufactured by Pacific Machinery Co., Ltd.).

About the process (2)

Step (2) is a step of preparing granules, that is, nonionic detergent granules, using the mixture obtained in step (1). In step (2), above the temperature at which component (c) can be neutralized, that is, at a temperature at which both component (b) and component (c) become liquid, the mixture obtained in step (1) is rotated while increasing looseness. Density, while performing the granulation process. The granulation operation is performed at such a temperature because the (a) component and (c) component react efficiently to generate a gelled product.

More specifically, in A) when step (1) is carried out using a mixed solution obtained by mixing component (b), component (c) and component (d), step (2) can be performed at the melting temperature of the mixed solution. Granulation operation; B) When step (1) is carried out using a mixed liquid composed of any two components of the three components (b), (c) and (d) and the remaining components, The granulation operation of the step (2) may be performed at a higher temperature of the melting temperature of the mixed liquid or the melting point of the residual component; or C) adding (b) component, (c) component and (d) component one by one, When the step (1) is carried out, the granulation operation of the step (2) can be carried out at a temperature equal to or higher than the highest melting point among the melting points of these compounds.

The "melting temperature" of the liquid mixture in this specification refers to the lowest temperature among the temperatures at which the liquid mixture composed of two or more components maintains the same liquid state as a whole. The melting temperature varies depending on the types of components constituting the mixture and the mixing ratio. The melting temperature in the present invention is, for example, preferably at most 100°C, more preferably at most 80°C, particularly preferably at most 70°C.

Here, as the temperature for performing the granulation operation, in order to promote the reaction, it is suitable if it is at least the temperature shown in any one of A) to C). The temperature shown in any one of C) is 0 to 50°C higher, especially preferably 10 to 30°C higher.

Furthermore, in order to promote the reaction, water can also be added appropriately in the step (1) or the step (2), or in the step (1) or the step (2), it is also possible to use an amount below the neutralization equivalent of the acid precursor An aqueous alkali solution (eg, aqueous sodium silicate, aqueous caustic soda, aqueous caustic potash, etc.) is added.

When this reaction occurs, the gelled product carrying (b) component is formed on the surface of (a) component, and it completes the role of binder in the granulation process of step (2), while the (a) component Component (b) is more strongly supported on the surface of the surface, and plays a role in suppressing bleeding. In addition, the temperature of the granulated material at the end of step (2) is not particularly limited, but it is preferably higher than the temperature shown in any one of A) to C) by 10°C or more, more preferably 20°C or more. Of course, in spite of this, the reaction is promoted in the process carried out at high temperature, but it is desirable to select a temperature suitable for industry. When this range is satisfied, since the gelation reaction is promoted, the desired granulated matter can be obtained efficiently, which is satisfactory.

Thus, in the granulation process of process (2), since it is necessary to adjust a mixer to a specific temperature, it is suitable to use the mixer which can adjust a temperature. For example, in a mixer equipped with a water jacket capable of flowing liquids such as warm water, the temperature of the warm water flowing in the water jacket can be easily adjusted to a predetermined temperature, that is, any of A) to C). A temperature above the temperature shown, so is suitable. Furthermore, in order to maintain the granulated material at the desired temperature at the end of the above step (2), it is of course necessary to properly control the temperature of the water jacket.

In addition, as a mixer, there is a stirring shaft in the center of a horizontal cylinder, and a stirring type mixer is equipped with a stirring blade on the stirring shaft. From the above-mentioned gelled product as a binder, tumbling granulation is efficiently performed. From the point of view, it is appropriate. As a stirring mixer having such a structure, there are, for example, a Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.), a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powretsu Co., Ltd. Manufacturing), etc., preferably have a stirring shaft in the center of the cylinder in a horizontal mixing tank, and a stirring blade is installed on the stirring shaft to carry out powder mixing, such as a レデイゲ mixer (Matsuzaka Technology Research ( Co., Ltd.), Prosia Mixer (made by Pacific Machinery Co., Ltd.). In this case, the Froude number defined by the following formula is preferably from 1 to 12, more preferably from 2 to 10, according to the rotation of the stirring blade of the stirring mixer. From the viewpoint of suppressing excessive stirring force and narrowing the particle size distribution of the granulated material, the Froude number is preferably 12 or less. In addition, from the viewpoint of improving the mixing efficiency, the Froude number is preferably 1 or more.

Here, the Froude number is defined as follows.

Fr=V ² /(R×g) (However, Fr represents the Froude number, V represents the peripheral speed (m/s) of the tip of the stirring blade, R represents the radius of rotation (m) of the stirring blade, and g represents the acceleration of gravity (m/s ² )).

In the step (2), the granulation time in the batch granulation for obtaining suitable granules and the average residence time in the continuous granulation are not particularly limited, but preferably 2 to 20 minutes, preferably 3 to 10 minutes. From the viewpoint of accelerating the neutralization reaction, the granulation time and the average residence time are preferably at least 2 minutes, and from the viewpoint of productivity, they are preferably at most 20 minutes.

About the surface coating process

In the present invention, in order to coat the surface of the granulated matter granulated in the step (2), there may be a surface coating step of adding fine powder as a surface coating agent. If the surface of the granulated matter is coated, the fluidity and non-caking property of the granulated matter tend to be improved, so it is preferable to add fine powder. If the surface coating agent is added in the early or middle stage of granulation, it will enter the inside of the granulate, and it will be lost after granulation to improve the fluidity and non-caking properties of the granulate. The post-granulation term referred to here is the point at which the average particle size of the granulated matter is granulated within an appropriate range, that is, 250 to 800 μm. In addition, the fine powder preferably has an average primary particle diameter of 10 μm or less. This means that when the fine powder is coated on the surface of the granulated matter, it may be 10 μm or less. For example, an aggregate of fine powder of 20 to 30 μm may be pulverized and coated in the coating step. When the average particle diameter is 10 μm or less, the coverage rate on the surface of the granulated matter is further increased, and desired nonionic detergent granules are easily obtained. The average particle size of the fine powder is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba Seisakusho Co., Ltd.), observation measurement with a microscope, and the like.

As the surface coating agent, aluminosilicates are preferred because they function as calcium ion traps during washing, and aluminosilicates with an average particle diameter of primary particles of 10 μm or less are particularly preferred. The aluminosilicate may be of any kind regardless of whether it is crystalline or non-crystalline.

In addition to aluminosilicates, inorganic micropowders such as calcium silicate, silica, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds, etc., with an average primary particle diameter of 10 μm or less are also suitable. of.

Specific examples of aluminosilicates include those exemplified as inorganic detergent builders and porous oil-absorbing carriers. In addition, metal soaps whose primary particle average particle size is 10 µm or less can also be used.

Among the above substances, one or more compounds selected from the group consisting of crystalline or non-crystalline aluminosilicates and calcium silicates are preferable.

The amount of the powder used is preferably from 0.5 to 20 parts by weight, more preferably from 1 to 15 parts by weight, particularly preferably from 2 to 10 parts by weight, based on 100 parts by weight of the granulated material. From the viewpoint of suppressing dust generation, the amount of the powder used is preferably 20 parts by weight or less based on 100 parts by weight of the granulated material. In addition, from the viewpoint of improving fluidity and non-caking properties, the powder is preferably used in an amount of 0.5 parts by weight or more relative to 100 parts by weight of the granulated product.

The apparatus used in the surface coating step is not particularly limited, and known mixers can be used, but the mixers exemplified in the above-mentioned steps (1) and (2) are preferable. In particular, the mixer used in the step (2) is suitably used.

Utilize as above operation (1) and (2), preferably utilize operation (1), (2) and surface coating operation, manufacture nonionic detergent granule among the present invention, but can utilize in operation (2) With the above-mentioned device, the step (2) and the surface coating step are carried out batchwise. When performing the step (2) and the surface coating step in a continuous manner, an apparatus that continuously performs raw material supply and granulated product discharge among these apparatuses can be used. In the case of carrying out the present invention in a batch manner, the steps (1) and (2) or the steps (1), (2) and the surface coating step can be carried out with the same device using the agitating mixer used in the step (2). . A part of the granulation is performed in the step (1), and after the completion of the step (1), the granulation is carried out by continuing stirring and mixing. When the steps (1), (2) and the surface coating step are carried out with the same apparatus, a stirring type mixing tank having a horizontal stirring shaft in the center of the mixing tank of a horizontal cylinder is particularly suitable.

In addition, when carrying out the present invention in a continuous manner, the step (1) and the step (2) can be carried out simultaneously with the same apparatus by using the agitation type mixer used in the step (2). In addition, if there is a structure in the axial direction that can divide the mixing tank of the stirring mixer with a horizontal stirring shaft in the center of the mixing tank of the horizontal cylinder (for example, inserting a partition), it can be continuously performed with the same device. Processes (1) and (2), process (2) and surface coating process, process (1) and process (2) and surface coating process.

In addition, the loading amount of the above-mentioned various detergent raw materials into the mixer is preferably 70% by volume or less of the total volume, no matter in which process, and whether it is in a batch type or in a continuous type. , preferably 15-40% capacity. From the viewpoint of the mixing efficiency of the detergent raw materials in the mixer, it is preferable that the charging amount is not more than 70 capacity % of the full capacity of the mixer.

Furthermore, in the present invention, the following additives can be used in the steps (1) and (2), or after the surface coating step.

(1) Bleach

For example, sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, etc. are mentioned.

(2) Enzymes

Although it will not specifically limit if it is an enzyme used for a detergent, Protease, cellulase, amylase, lipase etc. are mentioned as especially suitable enzyme.

(3) Powder of surfactant

For example, alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-alkene sulfonate, α-sulfonated fatty acid salt or ester salt, Powders of anionic surfactants such as alkyl or alkenyl ether carboxylates and soaps, powders of amphoteric active agents such as carbonyl betaine and sultaine, powders of cationic surfactants such as double long-chain quaternary ammonium salts wait.

(4) Others

As other additives, bluing agents, anti-caking agents, antioxidants, fluorescent dyes, photoactivated bleaching agents, perfumes, and re-pollution preventive agents can be mentioned. If they can be used in detergents, they are not used. special restrictions.

Furthermore, if the granulation method of the present invention is used, there is no restriction on (1) the composition in the granulation using the hydration of the cleaning active salt and (2) the composition in order to establish stable operability in the solidification/crushing method The detergent raw material composed of powder raw material and non-ionic active agent can be formed in any proportion, which has the advantage that it is difficult to be constrained by the composition.

In addition, in the following production method, the detergent granular composition (for example, JP-A-61-69897, JP-A-60-72999, JP-A-3-33199, Special Kaiping 3-146599, Special Kaiping 5-86400, Special Kaiping 61-76597, Special Kaiping 60-96698, Special Kaiping 3-115400, Special Kaiping 2-29500, Special Table 6-506720, Special Kaiping 4-81500 , JP-A-61-272300, JP-1-311200, JP-6-502212, etc.), the nonionic detergent particles obtained by the production method of the present invention can be blended in any proportion.

As the physical properties of the nonionic detergent granules obtained in the present invention, the following physical properties are suitable.

(1) Bulk density: 0.6~1.2g/ml, preferably 0.7~1.0g/ml. From the viewpoint of the solvent properties of the particles obtained, it is preferably 1.2 g/ml or less.

(2) Average particle diameter: preferably from 250 to 800 μm, most preferably from 300 to 600 μm. The average particle diameter was obtained by the method described later. From the viewpoint of the solvent properties of the obtained particles, it is preferably 800 μm or less, and from the viewpoint of suppressing dust generation, it is preferably 250 μm or more.

(3) Fluidity: The flow time is preferably at most 10 seconds, most preferably at most 8 seconds. The flow time is the time required to flow 100ml of powder from the hopper for bulk density measurement according to JIS K 3362. From the viewpoint of the processability of the obtained pellets, it is preferably 10 seconds or less.

(4) Caking property: the sieve passing rate is preferably above 90%, most preferably above 95%. The sieve pass rate was calculated|required by the method mentioned later. From the viewpoint of suppressing caking during storage, it is preferably 90% or more.

(5) Bleeding property: Visual evaluation described in Examples described later is preferably at least 2 grades, most preferably 1 grade. From the viewpoint of suppressing the adhesion of the powder containing the nonionic active agent to the equipment of the conveying system, grade 2 or higher is preferable.

(6) Weight increase rate: The weight increase rate is preferably at most 10%, more preferably at most 8%. The weight increase rate was calculated|required by the method mentioned later. From the viewpoint of suppressing the caking of detergent granules, it is preferably 10% or less.

(7) Solubility: The initial solubility is preferably at most 0.5%, most preferably at most 0.3%. After time, it is preferably at most 1.0%, most preferably at most 0.8%. Solubility (initial stage and elapsed time) was determined by the method described later. From the viewpoint of suppressing deposits on the object to be washed after low-temperature washing, the initial solubility is preferably 0.5% or less, and the temporal solubility is preferably 1.0% or less.

(8) Blocking property: The container remaining rate is preferably at most 20% by weight, more preferably at most 10% by weight, particularly preferably at most 5% by weight. As the measurement method, the method described below was used.

(9) Particle breaking strength: preferably at least 20 gf, most preferably at least 30 gf. As the measurement method, the method described below was used.

Hereinafter, the present invention will be described in detail according to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In addition, in the following examples, etc., heavy soda ash and 4A type zeolite are manufactured by Tosoh-(Co., Ltd.), and light soda ash is pulverized by using a pulverizer manufactured by Fuji Paudal to grind Tosoh-( Co., Ltd.) made of light soda ash crushed light soda ash. In addition, polyoxyethylene lauryl ether has an average added mole number of ethylene oxide = 8, a melting point of 15° C., and HLB = 10.14. As an amorphous aluminosilicate, an aluminosilicate manufactured by Kao Co., Ltd. was used, the composition was Na ₂ O·Al ₂ O ₃ 3SiO ₂ , the pore volume = 245 cm ³ /100 g, the specific surface area = 64 m ² /g, Oil absorption = 180ml/100g, water content = 26.5%, primary particle size = 0.05μm.

In addition, the builder used in the following Examples and the like has a pH value at 20° C. of a 1 g/l aqueous solution or dispersion of a porous oil-absorbing carrier.

Heavy soda ash: 11.1, crushed light soda ash: 11.0, 4A type zeolite: 9.8, amorphous aluminosilicate: 10.4, Glauber's salt: 7.1, crystalline silicate 11.5.

In addition, the melting points of nonionic active agents and the like used in the following Examples and the like are as follows. Polyoxyethylene lauryl ether is 15°C, polyethylene glycol is 55°C, palmitic acid is 63°C, and lauryl sulfate is 38°C.

Example 1

25 parts by weight of the nonionic active agent, 2 parts by weight of polyethylene glycol and 10 parts by weight of fatty acid described in Table 1 were heated to 70°C and mixed to prepare a mixed solution. Next, 29 parts by weight of heavy soda ash, 10 parts by weight of 4A zeolite type and 24 parts by weight of non-crystalline aluminosilicate were put into a redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 20 L, with water jacket). , start the stirring of the main shaft (150r/min) and the chopper (4000r/min). Warm water at 75° C. was flowed in the water jacket at 10 L/min. The above-mentioned mixed solution was charged into the mixer over 4 minutes, stirred for 6 minutes thereafter, and then discharged. The total charge is 4kg. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 2

The raw materials shown in Table 1 were charged in the same granulation method as in Example 1 to obtain nonionic detergent granules. Then, 8 parts by weight of 4A-type zeolite as a surface coating agent was put into the same Reddyke mixer, stirred for 1.5 minutes, and then discharged. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 3

25 parts by weight of the nonionic active agent and 2 parts by weight of polyethylene glycol described in Table 1 were heated to 75° C. and mixed to prepare a mixed liquid. Furthermore, 34 parts by weight of heavy soda ash, 10 parts by weight of 4A type zeolite and 24 parts by weight of amorphous aluminosilicate were put into a redeig mixer (manufactured by Matsuzaka Giken Co., Ltd., with a capacity of 20 L and a water jacket). , start stirring. Stirring was performed with a spindle (150r/min) and a chopper (4000r/min), and warm water at 75°C was flowed at 10L/min in the water jacket. The above-mentioned mixed solution was put into the mixer for 2.5 minutes, and stirred for 4 minutes. Next, 5 parts by weight of fatty acid was put in for 1.5 minutes, and then stirred for 4 minutes. Subsequently, 8 parts by weight of 4A-type zeolite was added as a surface coating agent, and the stirring was continued for 1.5 minutes before being discharged. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 4

34 parts by weight of heavy soda ash, 10 parts by weight of type 4A zeolite, and 24 parts by weight of amorphous silicon were put into a REDIGE mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 20 L, with a water jacket). Aluminate, start stirring. Stirring was performed with a spindle (150r/min) and a chopper (4000r/min), and warm water at 75°C was flowed at 10L/min in the water jacket. 25 parts by weight of the nonionic active agent and 2 parts by weight of polyethylene glycol were dropped into the mixer one by one at the same time, and the stirring was continued for 4 minutes. The time required for input is 2 minutes. Next, 5 parts by weight of fatty acid was added in 1.5 minutes, and stirring was continued for 6 minutes. Subsequently, 8 parts by weight of 4A-type zeolite as a surface coating agent was put in, stirred for 1.5 minutes, and then discharged. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 5

25 parts by weight of the nonionic active agent and 5 parts by weight of fatty acid listed in Table 1 were mixed at 75° C. to prepare a liquid mixture. Furthermore, 34 parts by weight of heavy soda ash, 10 parts by weight of 4A type zeolite and 24 parts by weight of amorphous aluminosilicate were put into a redeig mixer (manufactured by Matsuzaka Giken Co., Ltd., with a capacity of 20 L and a water jacket). , start stirring. Stirring was performed with a spindle (150r/min) and a chopper (4000r/min), and warm water at 75°C was flowed at 10L/min in the water jacket. 2 parts by weight of powdery polyethylene glycol described in Table 1 was put into the mixer, and stirring was continued for 6 minutes. Next, the above-mentioned liquid mixture was poured in for 4 minutes, and stirring was continued for 6 minutes. Subsequently, 8 parts by weight of 4A-type zeolite as a surface coating agent was put in, stirred for 1.5 minutes, and then discharged. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 6

25 parts by weight of the nonionic active agent and 5 parts by weight of fatty acid listed in Table 1 were mixed at 75° C. to prepare a liquid mixture. Furthermore, 34 parts by weight of heavy soda ash, 10 parts by weight of 4A type zeolite and 24 parts by weight of amorphous aluminosilicate were put into a redeig mixer (manufactured by Matsuzaka Giken Co., Ltd., with a capacity of 20 L and a water jacket). , start stirring. Stirring was performed with a spindle (150r/min) and a chopper (4000r/min), and warm water at 75°C was flowed at 10L/min in the water jacket. The above-mentioned liquid mixture was poured into the mixer over 4 minutes, and stirring was continued for 6 minutes. Next, 2 parts by weight of powdery polyethylene glycol recorded in Table 1 was dropped in, and stirring was continued for 2 minutes. Subsequently, 8 parts by weight of 4A-type zeolite as a surface coating agent was put in, stirred for 1.5 minutes, and then discharged. Table 3 shows the evaluation results of the nonionic detergent granules thus obtained.

Examples 7-13

Using the raw materials described in Table 1 and Table 2, nonionic detergent granules were obtained. The granulation method and the surface coating method are the same as in Example 2. Table 3 and Table 4 show the evaluation results of the obtained nonionic detergent granules.

Embodiment 14, Embodiment 15

Using the raw materials described in Table 5 and Table 6, nonionic detergent granules were obtained. The granulation method and the surface coating method are the same as in Example 2. Table 7 shows the evaluation results of the obtained nonionic detergent granules. Here, the "spray-dried granule" is used by mixing an alkaline builder and an alkaline porous oil-absorbing carrier. "Spray-dried particles" were obtained by spray-drying a 50% by weight slurry, and the composition described in Table 6 was used.

Example 16

25 parts by weight of the nonionic active agent, 2 parts by weight of polyethylene glycol, and 5 parts by weight of fatty acid described in Table 5 were heated to 70° C. and mixed to prepare a mixed solution. Next, 32 parts by weight of the mixed liquid, 40 parts by weight of heavy soda ash, 4 parts by weight of 4A type zeolite and 24 parts by weight of non Crystalline aluminosilicate. At this time, the total charge is 250Kg/h, the rotation speed of the main shaft is 3000r/min, and a fluid nozzle (2Kg/cm ² pressure) is used to spray the mixed liquid in the machine. Next, this mixed detergent raw material was continuously charged into a Rediger mixer KM-150D (manufactured by Matsuzaka Giken Co., Ltd., equipped with a water jacket) and granulated. At this time, the rotation speed of the main shaft was 105 r/min, the rotation speed of the shredder was 3440 r/min, and warm water at 75° C. was flowed at 10 L/min in the water jacket. In addition, the average residence time was 6.1 minutes.

Then, continuously drop 100 parts by weight of the above-mentioned granulated detergent raw material and 8 parts by weight of the 4A-type zeolite and mixed. At this time, the rotation speed of the main shaft was 130 r/min, the rotation speed of the shredder was 4000 r/min, and 75° C. warm water was flowed at 10 L/min in the water jacket. In addition, the average residence time was 1.5 minutes. Table 7 shows the evaluation results of the nonionic detergent granules thus obtained.

Example 17

The same detergent raw materials as those in Example 16 were continuously charged into a redide mixer KM-150D (manufactured by Matsuzaka Giken Co., Ltd., with a water jacket), and mixed and granulated simultaneously. At this time, the total charge is 250Kg/h, the rotation speed of the main shaft is 105r/min, the rotation speed of the shredder is 3440r/min, and 75°C warm water flows at 10L/min in the water jacket. In addition, the average residence time was 6.0 minutes. Using 1 fluid nozzle (2Kg/cm ² pressure), spray the mixture towards the area where the chopper rotates. The process of coating the surface of the granulated material was carried out in the same manner as in Example 16. Table 7 shows the evaluation results of the obtained nonionic detergent granules.

Comparative example 1

The raw materials shown in Table 2 were charged with the same granulation method and surface coating method as in Example 2 to prepare nonionic detergent granules. Table 4 shows the evaluation results.

Comparative example 2

25 parts by weight of the nonionic active agent described in Table 2 and 2 parts by weight of polyethylene were mixed at 75° C. to prepare a liquid mixture. 34 parts by weight of heavy soda ash, 10 parts by weight of 4A type zeolite and 24 parts by weight of amorphous aluminosilicate were put into a redeig mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 20L, with a water jacket), and Stir. Stirring was performed with a spindle (150r/min) and a chopper (4000r/min), and warm water at 75°C was flowed at 10L/min in the water jacket. Next, 5 parts by weight of fatty acid was charged into the mixer for 1.5 minutes, and stirring was continued for 4 minutes. Next, the above-mentioned mixed solution was poured in for 2.5 minutes, and stirring was continued for 6 minutes. Subsequently, 8 parts by weight of 4A-type zeolite as a surface coating agent was put in, stirred for 1.5 minutes, and then discharged. Table 4 shows the evaluation results of the nonionic detergent granules thus obtained.

The evaluation of the nonionic detergent granule obtained by the said Example etc. was performed as follows.

The bulk density is measured according to the method specified in JIS K 3362. The average particle size is measured from the weight fraction based on the size of the sieve after vibrating for 5 minutes using a standard sieve of JIS Z 8801. In addition, the fluidity of the powder is evaluated by the time required to flow 100ml of powder from the funnel for bulk density measurement specified in JIS K 3362.

In addition, the test method of caking property is as follows.

Caking test method

Using filter paper (Toyo Filter Paper No. 2), a box without a top of 10.2 cm in length x 6.2 cm in width x 4 cm in height was prepared, and the four corners were fixed with a stapler. 50 g of the sample is placed in this box, and the total weight of the acrylic resin plate and the lead plate (or iron plate) is placed on it 15 g+250 g. It was placed in a thermo-hygrostat with a temperature of 30° C. and a humidity of 80%, and after 7 days or 1 month, the caking state was judged. Judgment is performed by obtaining the pass rate as follows.

Passing rate

The sample after the test was poured gently on the metal mesh (or sieve, mesh 5mm×5mm), and the weight of the powder passing through the metal mesh was measured to obtain the passing rate with respect to the sample after the test.

In addition, the test method of exudation property is as follows.

The oozing state of the liquid component at the bottom (surface not in contact with the powder) of the filter paper subjected to the caking test was visually evaluated. The evaluation of oozing is judged on the basis of the stained area of the bottom, and it is graded as 1-5. The status of each level is as follows.

Grade 1: not wet.

Grade 2: 1/4 of the area is wet.

Grade 3: 1/2 degree area wet.

Grade 4: 3/4 of the area is wet.

Level 5: Wet all over.

The weight gain rate is the weight gain of the original sample expressed in percentage (%) after measuring the weight of the sample after storage for 7 days and after the caking test.

Regarding the dissolution rate, 0.83 g of the sample was sampled, added to 1 L of tap water at 10°C, stirred with an electromagnetic stirrer for 10 minutes, and then filtered through a 200-mesh metal mesh. Here, the term "initial stage and elapsed time" refers to the solubility after the caking test after storage for 7 days before the caking test.

The particle failure strength was studied as described below.

Arbitrary 1 granule is selected from the nonionic detergent granule of 1000-1400 micrometers sieved by the sieve, and the destruction intensity|strength of the granule is measured using the rheometer. In the same manner, the fracture strengths of a total of 10 particles were obtained, and the average value thereof was used as the particle fracture strength.

Adhesion was studied as described below.

250 g of the sample was placed in a metal cylindrical container with a diameter of 5 cm and a height of 15 cm without a top, and the sample and the container were dropped 5 times from a height of 5 cm. After leaving this to stand in an atmosphere of 40° C. for 24 hours, it was left to stand in an atmosphere of 5° C. for 24 hours, and the blocking property was evaluated by the residual ratio obtained as follows.

Residual rate

The container in which the treated sample was placed was turned upside down and lightly placed on the porcelain plate, and the weight of the powder dropped on the porcelain plate was measured. The proportion of the sample that did not fall and remain on the container was obtained from the weight of the powder dropped on the porcelain dish and the initial input amount, and the value was expressed as a percentage, which was regarded as the residual rate.

From the above results, it is clear that the nonionic detergent granules of Examples 1 to 17 obtained according to the production method of the present invention are excellent nonionic detergent granules with high bulk density and good fluidity. Furthermore, it can be seen that the non-caking property is good, there is no oozing, and the solubility in terms of weight gain is also excellent, but even when stored under high temperature and high humidity, the properties are slightly deteriorated. Furthermore, the long-term storage stability (caking property and exudation property after 1-month storage), particle breaking strength, and non-blocking property were good.

On the contrary, when the component (d) is not added, the long-term storage stability of the obtained detergent granules (caking property and exudation property after 1-month storage), granule breaking strength, and non-caking property ratio Differences obtained in Examples (Comparative Example 1). Moreover, when mixing (c) component and (a) component before (b), long-term storage property and non-caking property were inferior (comparative example 2). This is considered to be due to the failure to promote the formation of the gelled product.

The effect of the invention

According to the production method of the present invention, it is possible to produce high bulk density, excellent powder flow characteristics, non-blocking property and non-caking property, and non-ionic detergent particles without exudation, even if the above-mentioned properties are preserved under high temperature and high humidity, they are also excellent. Nonionic detergent granules that have good long-term storage stability and maintain easy solubility while suppressing hygroscopicity. In addition, the obtained nonionic detergent granules have very high detergency activity, and the concentration of the composition is effective, and when used as an additive, the degree of freedom in the composition of the basic detergent can be increased.

Table 1 (parts by weight) Example 1 2 3 4 5 6 7 8 nonionic detergent polyoxyethylene lauryl ether 25 25 25 25 25 25 25 25 polyethylene glycol PEG6000 (average molecular weight 8500) 2 2 2 2 2 2 2 2 fatty acid Palmitic acid 10 5 5 5 5 5 - 3 Alkyl Sulfate lauryl sulfate - - - - - - 10 - alkaline builder Heavy soda ash (average particle size 290μm) 29 34 34 34 34 34 34 twenty four 4A type zeolite (average particle size 3μm) 10 10 10 10 10 10 5 10 Alkaline porous oil-absorbing carrier Amorphous aluminosilicate (average particle size 10μm) twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four neutral or acidic builder Glauber's salt (average grain 280μm) - - - - - - - 10 Surface coating agent 4A type zeolite (average particle size 3μm) - 8 8 8 8 8 8 8

Table 2 (parts by weight) Example comparative example 9 10 11 12 13 1 2 nonionic active agent polyoxyethylene lauryl ether - -25 25 25 25 25 25 Aqueous solution of nonionic active agent polyoxyethylene lauryl ether moisture 30 15 - - - - - polyethylene glycol PEG6000 (average molecular weight 8500) 3 2 2 2 1 - 2 fatty acid Palmitic acid 5 5 5 5 5 5 5 alkaline builder Heavy soda ash (average particle size 290μm) twenty four 26 34 twenty four 37 40 34 Crushed heavy soda ash (average particle size 8μm) - 42 - - - - - 4A type zeolite (average particle size 3μm) 10 10 10 10 10 10 10 Crystalline silicate (average particle size 30μm) - - - 10 - - - Alkaline porous oil-absorbing carrier Amorphous aluminosilicate (average particle size 10μm) 29 - twenty four twenty four twenty two 20 twenty four Surface coating agent 4A type zeolite (average particle size 3μm) 8 8 - 8 8 8 8 Amorphous aluminosilicate (average particle size 10μm) - - 3 - - - -

table 3 Example 1 2 3 4 5 6 7 8 Water jacket temperature (℃) 75 75 75 75 75 75 40 75 Bulk density (g/ml) 0.81 0.83 0.83 0.83 0.83 0.81 0.83 0.83 Average particle size (μm) 440 420 425 410 415 395 410 415 Liquidity (seconds) 6.5 5.9 5.9 6.4 6.4 6.2 6.4 6.4 Caking ^* (%) 100 100 100 100 100 100 100 100 Caking ^** (%) 95 100 96 93 93 90 95 95 exudative ^* 1-2 1 1 1-2 1-2 1-2 1-2 1-2 exudative ^** 1-2 1 1-2 1-2 1-2 2 1-2 1-2 Weight gain (%) 3.1 2.2 3.2 3.0 2.4 1.8 2.8 3.5 Solubility Initial (%) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Elapsed time (%) 0.4 0.2 0.4 0.3 0.3 0.2 0.3 0.4 Particle failure strength (gf) 42 58 56 60 52 57 49 61 Adhesion (%) 25 0 0 0 0 0 0 0

^* : The value after 7 days of storage

^** : The value after saving for 1 month

Table 4 Example comparative example 9 10 11 12 13 1 2 Water jacket temperature (℃) 75 75 75 75 75 75 75 Bulk density (g/ml) 0.81 0.84 0.84 0.88 0.82 0.80 0.81 Average particle size (μm) 395 380 415 420 390 425 530 Liquidity (seconds) 6.2 6.6 6.1 6.2 6.3 6.9 8.1 Caking ^* (%) 100 100 100 100 100 100 100 Adhesion ^** (%) 100 100 100 95 93 72 78 exudative ^* 1 1 1 1-2 1-2 1-2 1-2 exudative ^** 1 1-2 1 1-2 1-2 3-4 3 Weight gain (%) 7.9 2.1 3.0 2.4 2.0 2.5 3.8 Solubility Initial (%) 0.1 0.1 0.1 0.1 0.1 0.1 1.0 Elapsed time (%) 0.2 0.3 0.2 0.2 0.4 0.3 1.2 Particle failure strength (gf) 51 48 62 54 45 34 48 Adhesion (%) 0 0 0 0 0 80 20

^* : The value after 7 days of storage

^** : The value after saving for 1 month

Table 5 (parts by weight) Example 14 15 16 17 nonionic active agent polyoxyethylene lauryl ether 25 25 25 25 polyethylene glycol PEG6000 (average molecular weight 8500) 2 2 2 2 fatty acid Palmitic acid 5 5 5 5 alkaline builder Heavy soda ash (average particle size 290μm) 20 20 40 40 4A type zeolite (average particle size 3μm) 4 4 4 4 Alkaline porous oil-absorbing carrier Amorphous aluminosilicate (average particle size 10μm) twenty four twenty four twenty four twenty four

Table 6 (parts by weight) Example 14 15 16 17 Spray dried particles*3 Type 4A Zeolite 12.9 13.9 - - Glauber's salt 5.0 5.0 - - sodium stearate 1.0 - - - Carboxymethylcellulose sodium salt 0.1 0.1 - - moisture 1.0 1.0 - - Surface coating agent 4A type zeolite (average particle size 3μm) 8 8 8 8 Water jacket temperature (℃) 75 75 75 75

^* Example 14: Bulk density 0.45 (g/ml), average particle diameter 245 (μm)

Embodiment 15: Bulk density 69 (g/ml), average particle diameter 215 (μm)

Table 7 (parts by weight) Example 14 15 16 17 Bulk density (g/ml) 0.78 0.85 0.86 0.85 Average particle size (μm) 395 380 425 415 Liquidity (seconds) 6.3 6.2 6.2 6.3 Caking (7 days storage) (%) 100 100 100 100 Caking (1 month storage) (%) 100 100 100 100 Exudation (7 days storage) 1 1 1 1～2 Exudation (preservation for 1 month) 1～2 1 1～2 1～2 Weight gain (%) 2.1 3.0 2.4 2.0 Solubility Initial (%) 0.1 0.1 0.1 0.1 Elapsed time (%) 0.4 0.2 0.2 0.3 Particle failure strength (gf) 62 60 57 56 Adhesion (%) 0 0 0 0

Claims (7)

1. A method for producing nonionic detergent granules, characterized in that adopting the following steps to obtain a bulk density of 0.6～1.2g/ml nonionic detergent granules, Step (1): preparation contains (a) alkaline builder and/or alkaline porous oil-absorbing carrier, (b) nonionic active agent and/or nonionic active agent aqueous solution, (c) can The acid precursor of the anionic surfactant that selects lamellar orientation, and (d) a water-soluble compound selected from polyether-based nonionic organic compounds or polyoxyethylene-type nonionic organic compounds with a melting point of 45°C or higher and an average molecular weight of 1,000 or higher. The process of a mixture of nonionic organic compounds, that is, (i) in the form of premixing (b) and (c) ingredients and adding to a mixer, (ii) a form in which (b) and (c) are added to the mixer one by one at the same time, and (iii) A form in which component (c) is added to the mixer after the addition of component (b) to the mixer starts or after addition is completed, and component (c) is added in any form selected from the group consisting of the above forms Mixer, the process of preparing a mixture, wherein the basic porous oil-absorbing carrier has a pH of 8 or more when it is a 1 g/L 20°C aqueous solution or dispersion liquid, and a pore volume of 100 to 100 according to the mercury intrusion method. 600cm ³ /100g, a specific surface area according to the BET method of 20 to 700m ² /g, an oil absorption of 100ml/100g or more according to JIS K 5101, and an average particle diameter or primary particle average particle diameter of 10μm or less. carrier; and Step (2): At a temperature above the temperature at which the acid precursor can be neutralized, the mixture obtained in the step (1) is rotated using a stirring type mixer, and the bulk density is increased while performing granulation to prepare granules, wherein , carry out step (2) above the temperature shown in the following (A), (B) or (C), (A) When the mixed solution obtained by mixing (b) component, (c) component and (d) component is used to carry out step (1), the melting temperature of the mixed solution, (B) When step (1) is performed using a mixture formed by combining any two of the three components (b), (c) and (d) and the remaining components, the mixture The higher temperature of the melting temperature or the melting point of the residual ingredient, (C) When step (1) is performed by adding (b) component, (c) component, and (d) component one by one, the melting point of these compounds is the highest melting point. 2. The production method according to claim 1, wherein the component (c) is selected from saturated or unsaturated fatty acids with 10 to 22 carbon atoms, alkyl sulfuric acid with 10 to 22 carbon atoms, fatty acids with 10 to 22 carbon atoms, A group consisting of α-sulfonated fatty acid and polyoxyethylene alkyl ether sulfuric acid with 10 to 22 carbon atoms, wherein the average added mole number of ethylene oxide is 0.2 to 2.0. 3. The production method according to claim 1 or 2, wherein the compounding amount of the component (c) is 5 to 100 parts by weight relative to 100 parts by weight of the component (b). 4. The production method according to any one of claims 1 to 3, wherein in the step (1), a neutral or acidic builder and/or spray-dried granules are further blended. 5. The production method according to any one of claims 1 to 4, wherein the compounding amount of the detergent raw material in the step (1) is selected from the following (A) or (B), (A) The total compounding amount of (b) component, (c) component and (d) component is 10 to 60 parts by weight, (a) component is 40 to 90 parts by weight, and a neutral or acidic auxiliary The lotion is 0-10 parts by weight, (B) The total compounding amount of (b) component, (c) component, and (d) component is 10 to 60 parts by weight, (a) component is 10 to 80 parts by weight, and is a neutral or acidic builder The agent is 0-10 parts by weight, and the spray-dried particles are 10-80 parts by weight. 6. The production method according to any one of claims 1 to 5, wherein the component (d) has a melting point of 45 to 100°C and an average molecular weight of 1,000 to 30,000. 7. The production method according to any one of claims 1 to 6, wherein the blocking property of the obtained nonionic detergent granules shows a container residual rate of 20%.