WO2004094313A1

WO2004094313A1 - Surface-treated particle of water-soluble inorganic compound, process for producing the same, and particulate detergent composition

Info

Publication number: WO2004094313A1
Application number: PCT/JP2004/005910
Authority: WO
Inventors: Hiroyuki Masui; Naoki Nakamura; Tatsuo Nagano; Kodo Horie; Satoshi Matsunaga; Katsuya Nagayasu; Satoru Nagata; Sumito Kinoe; Miyuki Miyake; Eri Hidai
Original assignee: Lion Corporation
Priority date: 2003-04-24
Filing date: 2004-04-23
Publication date: 2004-11-04
Also published as: KR101102273B1; JPWO2004094313A1; MY146571A; JP4753021B2; KR20060006915A

Abstract

Surface-treated water-soluble inorganic compound particles obtained by treating the surface of core particles of a water-soluble inorganic compound with an organic or inorganic, water-soluble polymer and further treating the surface of the resultant particles with a sparingly water-soluble compound. The surface-treated water-soluble inorganic compound particles do not agglomerate even when wetted under the conditions of a low water temperature and a low stirring force. The particles have excellent solubility during laundering. They have excellent flowability and can be prevented from adhering to a granulator during production.

Description

Specification

TECHNICAL FIELD The present invention relates to a surface-treated water-soluble inorganic compound particle, a method for producing the same, and a granular detergent composition.

The present invention relates to surface-treated water-soluble inorganic compound particles. In particular, the present invention relates to surface-treated water-soluble inorganic compound particles which are powder-mixed with a granular detergent composition as a powdering agent.

Background art

Conventionally, a method of granulating particles with a water-soluble polymer compound in order to solve various problems related to octundling, disintegration, storage stability, solubility, etc.

A method of coating the particle surface (Japanese Patent Application Laid-Open No. 2000-293354) has been proposed.

In the field of granular detergent compositions, a phenomenon is often observed in which detergent particles containing a surfactant gel and coagulate during washing in winter and remain undissolved. In particular, in recent years, the bath ratio has been reduced due to an increase in the size of a washing machine, and the amount of rinsing water has been reduced due to an energy-saving design. In addition, a method of pickling and using a powdered detergent has become widely used. For this reason, there is a tendency for detergent to remain undissolved when washing in winter using low-temperature water. In order to solve this problem, a method of coating the surface of detergent particles with a water-soluble polymer has been proposed (Japanese Patent Application Laid-Open No. Hei 7-224 999).

On the other hand, there has been proposed a technique of blending various particles in order to impart various functions to the granular detergent. In this case, the blended particles may interact with each other, leading to another problem of reducing the solubility of the granular detergent. In particular, when a powder of a water-soluble inorganic compound is mixed with detergent particles, when the water-soluble inorganic compound comes into contact with water and hydrates, the water-soluble inorganic compound violently agglomerates with the detergent particles to form aggregates, which remain undissolved. Had become.

In order to solve this problem, a technique has been proposed in which the detergent particle side is coated with a nonionic surfactant and the metal salt side is coated with a water-soluble organic substance solution and Z or solid powder (Japanese Patent Application Laid-Open (JP-A) No. 2002-110630). (Japanese Patent Application Laid-Open No. 2002-266600). However, the above proposal does not evaluate the solubility of the granular detergent and detergent aggregates under the coexisting condition of the clothes, and the detergent agglomeration is generated during actual washing with low stirring power and low-temperature water. It is not sufficient as a technique for suppressing the undissolved residue. Investigations from the viewpoint of controlling the heat of dissolution of water-soluble inorganic compounds are insufficient even in the point that nothing has been done.

Further, as a technique for solving the problems that occur when powders are mixed with each other, for example, water-insoluble powders or granulated materials such as bleach activators are converted into aqueous solutions having a functional group that reacts with polyvalent metal ions. After cross-linking with a polyvalent metal ion after coating with a conductive polymer compound (Japanese Patent Application Laid-Open (JP-A) No. 115-15042, Japanese Patent Laid-Open No. 63-135022) Has been done. However, these techniques are also aimed at improving storage stability and form stability when blended in a multi-aqueous composition, and do not suppress the formation of aggregates during dissolution.

In addition, various coating techniques have been proposed for water-soluble inorganic compound particles intended to be mixed with powder in a granular detergent.

For example, a technique has been proposed in which a water-soluble inorganic compound is granulated with a water-soluble polymer compound to improve the dissolution rate of the granules and the dispersibility during washing (Japanese Patent Application Laid-Open No. 63-209398). Bulletin, Japanese Translation of PCT International Publication No. 2000-501250). In addition, a technique of mixing a plurality of poorly water-soluble inorganic compounds such as alkali metal silicates with a water-soluble inorganic compound, or combining these, or spraying a concentrated silicate solution onto a water-soluble inorganic compound carrier to coat the same. The following techniques have been proposed (Japanese Patent Application Laid-Open Nos. H8-600200, H7-124750, and 2000-34496).

However, these coating techniques also focus on the storage stability of the particles and the improvement in detergency, and suppress the formation of detergent aggregates when washing with low-temperature water, and reduce the undissolved residue. It is unknown whether it can be prevented.

On the other hand, to solve the problem of the solubility of the water-soluble inorganic compound, a technique of coating the inorganic compound with a poorly water-soluble (organic) compound has been proposed. For example, as a technique for controlling the dissolution rate, a coating method using a higher alcohol has been proposed (Japanese Patent Laid-Open No. 2001-501501).

In addition, under conditions where stirring power is sufficiently applied, undissolved residue when washing with cold water As a technique for improvement, a method of coating with a fatty acid salt (Japanese Unexamined Patent Publication No. Hei 11-22998, Japanese Unexamined Patent Publication No. Hei 10-237498) is disclosed. A method of coating with an acid precursor of an activator and neutralizing the surface at the same time has been proposed (Japanese Patent Application Laid-Open No. 2001-81498, Japanese Patent Application Laid-Open No. Hei 10-158896) Gazette), but the effect is not as clear.

Further, as another coating technique in the field of granular detergents, a detergent composition having a fluidity improving effect and a fine powder formation suppressing effect by coating a detergent component with an aluminosilicate and a water-soluble polymer, and a silicon dioxide particle and a water-soluble Granular detergents with excellent storage stability, which are coated with a conductive polymer, have been proposed (Japanese Patent Application Laid-Open No. 2000-500583, Japanese Patent Application Laid-Open No. Hei 6-172880). No.).

In addition, granules are prepared by variously combining anionic surfactants, nonionic surfactants, water-soluble inorganic compounds, water-soluble binders such as polyethylene glycol, etc., which are usually used in granular detergent compositions, to prepare enzymes and bleaching agents. A method for stabilizing the activity of the surfactant, a method for suppressing the hydrolysis of the surfactant itself, and the like have also been proposed (Japanese Patent Application Laid-Open Nos. 6-192697 and 4-157040). No. 0, Japanese Unexamined Patent Publication (Kokai) No. 3-266569 /). However, the methods described in these documents are not sufficiently effective in suppressing the formation of detergent agglomerates and preventing the undissolved residue during washing using low-temperature water. .

As described above, a water-soluble inorganic compound that can efficiently prevent the formation of detergent agglomerates that occurs when washing under low-temperature water and with insufficient stirring power, and that exhibits excellent solubility during washing. There has been a demand for a particulate detergent composition comprising the particles and the particles, and having excellent fluidity and non-solidification properties after long-term storage. Disclosure of the invention

The present invention does not form agglomerates even when wet at low water temperature and low stirring power, shows excellent solubility during washing, has excellent fluidity, and is suitable for use in a granulator during production. It is an object of the present invention to provide surface-treated water-soluble inorganic compound particles capable of preventing adhesion. Further, the granular detergent composition containing these particles is excellent in fluidity and non-solidification after long-term storage. The present inventors have proposed a surface-treated water-soluble inorganic compound particle obtained by treating a surface of a water-soluble inorganic compound core particle with an organic or inorganic water-soluble polymer compound, and further treating the treated surface with a poorly water-soluble compound. By doing so, it was found that the above objectives could be achieved.

That is, the following invention is provided.

[1] A water-soluble inorganic compound core particle is surface-treated with an organic or inorganic water-soluble polymer compound as a first surface treating agent, and the treated surface is a second water-insoluble compound as a second surface treating agent. Surface-treated water-soluble inorganic compound particles treated with.

[2]. A water-soluble inorganic compound core particle, a first surface treatment section containing a water-soluble polymer compound formed on a part or the whole surface of the particle, and a part or a part on the surface of the first surface treatment part. The surface-treated water-soluble inorganic compound particles according to [1], further comprising a second surface-treated portion containing a poorly water-soluble compound formed on the entire surface.

[3]. The first surface treatment portion exhibits exothermicity in the process of dissolving or dispersing in water; the second surface treatment portion exhibits endothermicity in the process of dissolving or dispersing in water; 2. The surface-treated water-soluble inorganic compound particles according to [2], wherein the entire surface-treated portion comprising the second surface-treated portion exhibits endothermic properties in the process of dissolving or dispersing in water.

[4]. The surface-treated water-soluble inorganic compound particles according to any one of [1] to [3], wherein the water-soluble inorganic compound core particles are sodium carbonate or potassium carbonate.

[5]. The water-soluble polymer compound is characterized by being one or more selected from pinyl polymer compounds, polysaccharides, derivatives thereof, and polyester polymer compounds [1] to [1]. 4] The surface-treated water-soluble inorganic compound particles according to any one of the above.

[6]. It is characterized in that the water-soluble polymer compound is a compound having a lipoxyl group [1] ~! : The surface-treated water-soluble inorganic compound particles according to any one of 4).

[7]. The surface-treated water-soluble inorganic compound particles according to any one of [1] to [4], wherein the water-soluble polymer compound is water glass.

[8]. The surface-treated water-soluble inorganic compound particles according to any one of [1] to [: 7], wherein the poorly water-soluble compound is an anionic surfactant acid precursor and Z or a salt thereof.

[9] The surface-treated water-soluble inorganic compound particles according to [8], wherein the anionic surfactant acid precursor is a fatty acid. [10]. The surface-treated water-soluble inorganic compound particle according to any one of [1] to [: 9], which is an alkaline agent for blending a granular detergent composition.

[11]. A method for producing surface-treated water-soluble inorganic compound particles, comprising the following first step and second step.

First step: a step of adding an aqueous solution of a water-soluble polymer compound to the core particles of the water-soluble inorganic compound and treating the surface of the core particles of the water-soluble inorganic compound with the water-soluble polymer compound.

Second step: a step of adding a poorly water-soluble compound to the water-soluble inorganic compound core particles treated in the first step, and subjecting the particles to a surface treatment.

[12] The production method according to [11], wherein the poorly water-soluble compound is an anionic surfactant acid precursor.

[13]. The method according to [12], wherein the temperature of the surface-treated water-soluble inorganic compound particles immediately after the end of the second step is equal to or higher than the melting point of the acid precursor of the dione surfactant.

[14]. (A) The surface-treated water-soluble inorganic compound particles according to any one of [1] to [10], and (b) a surfactant and surfactant-containing particles containing an inorganic compound. A granular detergent composition characterized by the following.

[15], (b) The granular detergent composition according to [14], wherein the surfactant-containing particles contain a water-soluble polymer compound.

[16]. (A) the amount of the poorly water-soluble compound in the surface-treated water-soluble inorganic compound particles is less than 10% by mass, and (b) the amount of the surfactant in the surfactant-containing particles is 10% by mass. [15] The granular detergent composition according to [14] or [15], which is 50 to 50% by mass.

[171. [1] ~! A washing method comprising: performing a washing with the laundry containing the surface-treated water-soluble inorganic compound particles according to any one of [1] to [10] at a bath ratio of 7 to 15 1 ^ and a washing temperature of 5 to 12 ° C. BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 is a diagram showing the relationship between the amount of heat absorbed during dissolution and dispersion of the surface treatment part and the maximum temperature rise measured by the amount of heat generated by wetting. BEST MODE FOR CARRYING OUT THE INVENTION

The surface-treated water-soluble inorganic compound particles, which are the first surface treatment agent of the present invention, are obtained by subjecting water-soluble inorganic compound core particles to a surface treatment with an organic or inorganic water-soluble polymer compound, and further treating the treated surface with a poorly water-soluble compound. It is processed by. Water-soluble inorganic compound

The water-soluble inorganic compound of the present invention has a solubility in water at 5 ° C of 1 g / 100 g or more, preferably 2 g Z100 g or more, more preferably 3 g Z100 g or more. Means a water-soluble inorganic compound. There is no particular limitation as long as such a water-soluble inorganic compound is used, and one or a combination of two or more can be used as appropriate.

Preferred water-soluble inorganic compounds include those generally used as a washing builder. Such compounds include carbonates, bicarbonates and sesquicarbonates, sulfates and sulfites, phosphates and polycondensed phosphates, silicates, nitrates and nitrites, chlorides and the like. Among these, carbonates, sulfates, polycondensed phosphates and the like are more preferred, and sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium tripolyphosphate and the like are particularly preferred.

As the water-soluble inorganic compound, a water-soluble inorganic salt in which the pH of a saturated aqueous solution at 5 ° C is 8 or more can be more preferably used from the viewpoint of contribution to cleaning performance. Complex salts of inorganic salts with other water-soluble inorganic salts can also be suitably used, such as berkeite, which is a complex salt of sodium carbonate and sodium sulfate. It is. The water-soluble alkali inorganic salts can be used alone or in an appropriate combination of two or more.

When the water-soluble inorganic compound is moistened under low stirring to form an agglomerate, the coagulation of hydrate crystals of the water-soluble inorganic compound is deeply involved. It is preferable to apply the present invention to a substance that easily becomes a hydrate crystal at a temperature lower than 20 ° C. As such, most preferred are inorganic salts such as sodium carbonate and carbonated carbonate, and neutral inorganic salts such as sodium sulfate. The water-soluble inorganic compound core particles can be obtained by a conventional method, and the average particle diameter is preferably from 100 to 150 m, more preferably from 200 to 100 m. If the average particle diameter is less than 10, surface treatment with a water-soluble polymer compound may be difficult, and if it exceeds 150, the solubility of the water-soluble inorganic compound may decrease. As such water-soluble inorganic compound core particles, commercially available ones can be appropriately used. The average particle size is determined by a measuring method described in Examples described later. There are various grades of commercially available water-soluble inorganic compound core particles, but they do not limit the use of the present invention. For example, water-soluble inorganic salts containing impurities mixed in the production process, storage stabilizers for stabilizing quality, and antioxidants are also included in the scope of the present invention. Organic water-soluble polymer compound

The organic water-soluble high molecular weight compound as the second surface treatment agent used for the surface treatment of the water-soluble inorganic compound is 0.1 lg or more, preferably 0.2 g with respect to 100 g of water at 40 ° C. Above, more preferably a polymer compound that is uniformly mixed with water at a concentration of 2 g or more. The organic water-soluble polymer compound is not particularly limited as long as it is an organic water-soluble polymer compound, and may be used alone or in an appropriate combination of two or more.

Examples of the organic water-soluble polymer compound include a natural polymer compound, a semi-synthetic polymer compound, and a synthetic polymer compound. Specifically, vinyl polymer compounds, polysaccharides, polyether polymer compounds, polyester polymer compounds, peptide polymer compounds, polyurethanes, and derivatives thereof can be used. Among them, it is preferable to use one selected from a biel-based polymer compound, a polysaccharide, a derivative thereof, and a polyester-based polymer compound alone or in an appropriate combination of two or more.

Examples of the vinyl polymer compound include a pinyl polycarboxylate (acrylic acid polymer), a biel polysulfonate, a polyvinyl pyridine salt, and a polybilimidazolium salt. Various natural or synthetic polysaccharides can be used as the polysaccharide.

Examples of polyester-based polymer compounds include terephthalic acid and ethylene dali. Copolymers and copolymers with Z or propylene glycol units or turbomers. Examples of these include commercially available TeX care 4291 (manufactured by Clariant), TeX care SRN-300 (manufactured by Clariant), and the like.

Specific examples of peptide-based molecular compounds or derivatives thereof include gelatin, casein, albumin, collagen, polyglutamate, polyaspartate, polylysine, polyarginine, and derivatives thereof.

Examples of the polyurethane include a water-soluble polyurethane and the like. In addition, other water-soluble polymer compounds such as polyethylene glycol can also be used. Particularly, since the water-soluble inorganic compound is easily hydrated, the water-soluble inorganic compound is surface-treated with a water-soluble organic polymer compound. It is preferable that a material that exerts a waterlogging action in an initial stage of contact with water under the state of being in contact with water. Examples of the water-soluble organic polymer compound having such properties include those having a hydrophilic functional group such as anionic, amphoteric, and nonionic.

Examples of the water-soluble organic polymer compound having an anionic group include a polymer compound having a carboxyl group and a sulfo group, and a water-soluble polysaccharide having an anionic group.

Examples of the water-soluble organic polymer compound having a hydroxyl group include a monomer such as acrylic acid, maleic acid, itaconic acid, aconitic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid, or citraconic acid. And vinyl salts thereof, and copolymers of these monomers with other vinyl monomers and vinyl polycarboxylic acids (salts) such as salts thereof.

Examples of the water-soluble polymer compound having a sulfo group include monomers obtained by polymerizing monomers such as acrylamidopropanesulfonic acid, methacrylamidopropanesulfonic acid, and styrenesulfonic acid, and salts thereof, and these polymers and other polymers. And vinyl-based polysulfonic acids (salts) such as copolymers with vinyl-based polymers and salts thereof.

Examples of the water-soluble polysaccharide having an anionic group include polyuronates, For example, there may be mentioned formate, polyaspartate, lagenanan, hyaluronate, chondroitin sulfate, carboxymethylcellulose and the like.

Examples of the amphoteric water-soluble polymer compound include a copolymer of a vinyl monomer having an anionic group and a vinyl monomer having a cation group, a carboxybetaine group or a sulfovinyl group. Biel-based amphoteric polymer having

And acrylic acid Z-dimethylaminoethyl methacrylic acid copolymer, acrylic acid, and methylaminoethyl methacrylic acid copolymer.

Examples of the nonionic water-soluble polymer compound include synthetic polymer compounds such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polypinylethyl ether, and polyethylene glycol, hydroxyethyl cellulose, guar gum, dextran, pullulan, and the like. Polysaccharides.

Among these, compounds that have excellent water immersion at the initial stage of contact with water and generate heat when dissolved or dispersed in water are preferred. In view of this point, it is preferable to use a vinyl polymer having a carboxylic acid group or a sulfo group, and particularly preferable are vinyl polycarboxylic acids having a high anionic group content per unit mass. Specifically, polyacrylic acid salts, acrylic acid-Z maleic acid copolymer salts, acrylic acid-Z itaconic acid copolymer salts, alkyl acrylate copolymer salts, and derivatives thereof are most suitable.

The weight average molecular weight of the organic water-soluble polymer compound of the present invention is 500 or more, preferably 1, 000 to 1, 000, 0000, more preferably 1, 000 to 2, 0 0, 0 0 0. In addition, the average molecular weight of polyethylene glycol in the present invention indicates the average molecular weight described in the standard of cosmetic raw materials (the second edition). The weight average molecular weight of the organic water-soluble polymer compound in the present invention is a value measured by gel permeation chromatography using polyethylene dalicol as a standard substance.

The method for surface-treating a water-soluble inorganic compound with an organic water-soluble polymer compound is not particularly limited. For example, a method in which an organic water-soluble polymer compound is added to a water-soluble inorganic compound, mixed or coated, or the like can be used. It is preferable to use an organic water-soluble polymer compound as an aqueous solution for surface treatment. This aqueous solution is preferably added dropwise or spray-added to the water-soluble inorganic compound in a stirred and fluidized state. Inorganic water-soluble polymer compound

On the other hand, the inorganic water-soluble polymer compound is a compound which is uniformly miscible with water at a concentration of 0.1 g or more, preferably 0.2 g or more, more preferably 2 g or more at 100 ° C. of water at 40 ° C. It is. There is no particular limitation as long as such an inorganic water-soluble polymer compound is used, and one kind may be used alone, or two or more kinds may be used in appropriate combination. As the inorganic water-soluble polymer compound, a compound obtained by subjecting a solution containing a precursor compound of a metal alkoxide to a hydrolysis / condensation polymerization reaction is preferable, and a silicate is particularly preferable.

Silicate has long been incorporated into stones and is known as water glass. Based on its structure, it can be classified according to the form of anions (Friedrich Liebau, "Structural Chemistry of Si 1 icates "p 72, Springer-Verlag, 1985).

In detail, it can be classified by the number of bridging oxygens of the oxygen bonded to Si (S i— O— S i), and the number of bridging oxygens is 4, 3, 2, 1, 0, and Q 4 Classified into Q3, Q2, Ql and Q0 units (Y. T sunawa ki, N. I wamo to, T. Hattori and A. M its ubishi, J. No nCryst. Solids, vo 1 44, p 369 (198 1)).

The silicate contains Q2 unit and / or Q3 unit in order to sufficiently exhibit the treatment effect, and the Si ₂ ZM _{2 2} molar ratio (where M represents an alkali metal) is 1. Alkali metal silicates having 6 to 4, preferably 2 to 3.5 are preferred, and sodium silicate is particularly preferred.

The method for surface-treating the water-soluble inorganic compound with the inorganic water-soluble polymer compound is not particularly limited. For example, a method of adding, mixing or coating an inorganic water-soluble polymer compound to a water-soluble inorganic compound can be used. It is preferable to use an inorganic water-soluble polymer compound as an aqueous solution for surface treatment. This aqueous solution is preferably added dropwise or spray-added to the water-soluble inorganic compound in a stirred and fluidized state. Poorly water-soluble compound

The poorly water-soluble compound used in the present invention is a compound having a solubility in water at 20 ° C. of less than 2 g / 100 g, preferably less than 1 g / 100 g, more preferably less than 0.1 g / 100 g. Those having a water-repellent action at the initial stage in contact with are preferred. Further, an organic compound having a melting point of 200 ° C. or lower, preferably 0 to 160 ° C., more preferably 20 to 8 ° λ, and still more preferably 40 to 60 ° C. is suitable. The poorly water-soluble compounds can be used alone or in an appropriate combination of two or more.

Examples of poorly water-soluble compounds include higher fatty acids, dicarboxylic acids, higher alcohols, higher alcohols having an HLB of 5 or less, preferably 3 or less, alkylene oxide adducts of higher fatty acids, higher fatty acid esters, and glycerides of higher fatty acids. I can do it.

As the higher alcohol, those having a carbon chain length of 12 to 22 carbon atoms, more preferably 14 to 18 carbon atoms are suitable, and specifically, dodecanol, tetrade phenol, hexade phenol, octadecanol and the like are preferable. Is mentioned.

As an alkylene oxide adduct of a higher alcohol or fatty acid having an HLB of 5 or less, preferably 3 or less, a 1-3 mol ethylene oxide adduct of an alcohol or fatty acid having 16 to 22 carbon atoms is preferable. Examples thereof include a 1 mol ethylene oxide adduct of hexadenicol, a 3 mol ethylene oxide adduct of octadecanol, and a 1 mol ethylene oxide adduct of palmitic acid.

As higher fatty acid esters, methyl esters or ethyl esters such as palmitic acid, myristic acid, stearic acid, arachidic acid, and behenic acid are suitable. Di or tridalicelide is preferred.

In addition, since it absorbs heat during the initial wetting to control the heat generation of the water-soluble inorganic compound, and gradually becomes water-soluble due to a neutralization reaction with the water-soluble inorganic compound when washed, anion is a poorly water-soluble compound. It is preferred to use a surfactant acid precursor. As the anionic surfactant acid precursor, any anionic surfactant acid precursor can be suitably used. As anionic surfactant acid precursors, saturated or Are unsaturated fatty acids (average carbon chain length of 8 to 22), linear or branched alkyl (average carbon chain length of 8 to 18) benzenesulfonic acid, long chain alkyl (average carbon chain length of 10 to 20) sulfone Acid, long-chain olefin (average carbon chain length 10-20) Sulfonic acid, long-chain monoalkyl (average carbon chain length 10-20) Sulfuric acid ester, polyoxyethylene (average degree of polymerization 1-10) length Chain alkyl (average carbon chain length: 10 to 20) Ether sulfate, polyoxyethylene (average degree of polymerization: 3 to 30) Alkyl (average carbon chain length: 6 to 12) Phenyl ether sulfate, α-sulfo Examples include fatty acids (average carbon chain length of 8 to 22), long-chain monoalkyl, dialkyl or sesquialkyl phosphoric acid, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphoric acid, and the like. The anionic surfactant acid precursor is preferably a saturated or unsaturated fatty acid (average carbon chain length of 8 to 22), and more preferably has a carbon chain length of 8 to 18 carbon atoms. Specific examples include saturated fatty acids such as acetic acid, lauric acid, myristic acid, and palmitic acid, and unsaturated fatty acids such as oleic acid. Among them, saturated fatty acids having 12 to 18 carbon atoms are preferable from the viewpoint of storage stability, and rapaulinic acid is more preferable in consideration of productivity.

The method of surface-treating the water-soluble inorganic compound surface-treated with the first surface-treating agent with a poorly water-soluble compound is not particularly limited. For example, a method in which a poorly water-soluble compound is added to the surface-treated water-soluble inorganic compound, mixed or coated, or the like can be used. A method is preferred in which the poorly water-soluble compound is melted into a liquid state, and the liquid is dropped or spray-added to the surface-treated water-soluble inorganic compound in a stirred and fluidized state.

The amounts of each component in the surface-treated water-soluble inorganic compound particles of the present invention are shown below. The water-soluble inorganic compound is preferably used in an amount of 60 to 99.8% by mass, particularly preferably 70 to 97% by mass, based on the total amount of the surface-treated water-soluble inorganic compound particles. If the amount of the water-soluble inorganic compound is less than 60% by mass, the alkali agent may be insufficient. On the other hand, if the amount exceeds 99.8% by mass, the amount of the treating agent is too small, and sufficient surface treatment cannot be performed. May not be.

The organic water-soluble polymer compound is preferably used in an amount of 0.1 to 10% by mass, particularly 0.5 to 8% by mass, based on the core particles of the water-soluble inorganic compound. If it is less than 0.1% by mass, In some cases, the effect of the surface treatment may not be obtained. When the amount exceeds 10% by mass, the amount of the inorganic compound may be too small.

When the inorganic water-soluble polymer compound is blended, the inorganic water-soluble polymer compound is preferably used in an amount of 1 to 30% by mass, particularly preferably 10 to 28% by mass, based on the core particles of the water-soluble inorganic compound. If the amount is less than 1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 30% by mass, the amount of the inorganic compound may be too small.

The poorly water-soluble compound is preferably used in an amount of 0.1 to 10% by mass, particularly 2 to 8% by mass, based on the water-soluble inorganic compound core particles surface-treated with the first surface treating agent. If the amount is less than 0.1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the inorganic compound may be too small.

In addition, as other components, a surfactant, an optional component of the (b) surfactant-containing particles described below, and the like may be contained as long as the effects of the present invention are not impaired. Surface-treated water-soluble inorganic compound particles

The surface-treated water-soluble inorganic compound particles of the present invention are obtained by subjecting water-soluble inorganic compound core particles to a surface treatment with an organic or inorganic water-soluble polymer compound, and further treating the treated surface with a poorly water-soluble compound. The surface of the present invention refers to a water-soluble inorganic compound particle group (secondary particles or (Including agglomerated particles). In the case of the water-soluble inorganic compound particle group, the depth of the minute concave portions on the surface is 0.01 to 50 m.

The water-soluble polymer compound and the poorly water-soluble compound on the surface of the water-soluble inorganic compound core particles form a layer by the presence of the water-soluble polymer compound on the surface of the water-soluble inorganic compound core particles. The poorly water-soluble compound may be present in the part, or may be in a randomly mixed state. From the viewpoints of solubility and storage stability, it is preferable that the outermost layer of the surface-treated water-soluble inorganic compound particles contains more hardly water-soluble compounds than water-soluble polymer compounds. Further, from the viewpoint of manufacturability, it is preferable that a larger amount of the water-soluble polymer compound is present near the surface of the core particles of the water-soluble inorganic compound than the hardly water-soluble compound.

A particularly preferred structure of the surface-treated water-soluble inorganic compound particles is a water-soluble inorganic compound core particle. And a water-soluble polymer compound formed partially or entirely on the surface of the particles.

This is a structure having a first surface treatment section and a second surface treatment section containing a poorly water-soluble compound formed on a part or the whole surface of the first surface treatment section.

In particular, core particles of a water-soluble inorganic compound such as a carboxylate usually become alkaline when they come into contact with water or a water-soluble polymer solution. Therefore, when the poorly water-soluble compound is an acid precursor of an anionic surfactant such as a higher fatty acid, it is neutralized on the particle surface by the second surface treatment. When the amount of the acid precursor of the anionic surfactant to be added is relatively large, the neutralization reaction does not occur partially and may remain in the form of the acid precursor. The neutralization state of the acid precursor of the anionic surfactant can also be examined by a differential scanning calorimetry (Differential Scanning Calorimeter try; etc.). Since the acid precursor of the agent can be completely neutralized or partially neutralized on the particle surface, a second surface treatment part is formed with the anionic surfactant acid precursor and Z or a salt thereof. However, in any case, the particles can be suitably used as the surface-treated water-soluble inorganic compound particles in the present invention.The first surface-treated portion and the second surface-treated portion may impair the effects of the present invention as other components. Various additives such as a binder, a dispersant, a solubilizer, a pH adjuster, and a surfactant other than the poorly water-soluble compound may be appropriately contained as long as the surfactant is not contained. Surface-treated water-soluble inorganic compound particles In the above, the content is preferably less than 10% by mass, more preferably 5% by mass or less, further preferably 1% by mass or less. It is not included in the amount of the activator.

In the present invention, further, the first surface treatment portion exhibits exothermicity in the process of dissolution or dispersion in water, the second surface treatment portion exhibits endothermicity in the process of dissolution or dispersion in water, and the first surface treatment. It is preferable that the entire surface treatment part consisting of the part and the second surface treatment part shows endothermicity in the process of dissolving or dispersing in water.

By having such characteristics, aggregates formed between the core particles of the water-soluble inorganic compound and the detergent particles are suppressed, and the dissolution and heat generation of the water-soluble inorganic compound are controlled at the initial stage of contact with low-temperature water, Also dissolves quickly during washing with agitation, even with low agitation Characteristics can be remarkably exhibited.

Agglomerates formed between the water-soluble inorganic compound core particles and the detergent particles are considered as follows. Many water-soluble inorganic compounds which are powder-blended with the granular detergent composition generate a lot of heat upon contact with water. For example, the heat of dissolution of sodium carbonate is-24.57 kJ / mo 1 (described in General Chemical Industrial Products, SODA Ash Technical & Handling Guide), hydration of sodium sulfate The heat is 79.58 kJ / mo 1 (described in Chemical Handbook). This is due to the extremely large amount of heat generated by hydration in the process of dissolving the water-soluble inorganic compound in water, This is a characteristic due to the fact that the heat generated by hydration to become inorganic ions greatly exceeds the endotherm required for collapse.

When a water-soluble inorganic compound having such properties is supplied to a washing tub together with a granular detergent and is made wet by low-temperature water, the heat is generated violently, and the temperature near the particles rises. This increase in temperature causes the nearby detergent particles to change from a solid state to a liquid crystal state, causing gelation, while also promoting the dissolution of the inorganic compound itself to form a locally supersaturated dissolved state. When the supersaturated inorganic compound is cooled with low-temperature water before being stirred with a large amount of water, it forms hydrate crystals and condenses. As a result, an agglomerate containing the gelled detergent particles is formed.

In order to suppress the formation of the aggregates, it is effective to suppress the heat generation when the water-soluble inorganic compound causing gelation and hydration coagulation of the detergent particles is dissolved in water. In other words, it is necessary to have a treatment that has the property of cutting off the hydration of the water-soluble inorganic compound that generates heat during the dissolution process or removing the heat generated by the hydration. On the other hand, heat generation is effective in promoting the dissolution process, so in order to ensure the property that it dissolves quickly during washing, it completely shuts off contact with water and completely removes heat of hydration. Processing that takes away is not appropriate.

In order to achieve both of these, the first surface treatment section shows heat-generating property in the process of dissolving or dispersing in water, the second surface treatment section shows endothermic property in the process of dissolution or dispersion in water, By making all the surface treatment sections including the treatment section and the second surface treatment section endothermic during the process of dissolving or dispersing in water, the dissolution and heat generation of the water-soluble inorganic compound core particles can be controlled, and During the washing in which the stirring power is applied, the first surface treatment section which can impart the property of rapidly dissolving even under low stirring shows exothermicity in the process of dissolving or dispersing in water, and the second surface treatment section Although it shows endothermic properties, the specific amount of heat depends on the type and amount of treatment agent used, the balance between the first surface treatment unit and the second surface treatment unit, and the treatment conditions. The calorific value of the entire surface treatment part comprising the first surface treatment part and the second surface treatment part is endothermic, preferably 30 to 80 J / g particles, more preferably 40 to 70 J / g particles. The JZg particles mean the amount of heat (J) per gram of the inorganic compound particles (the same applies to the following description).

Further, it is preferable that the first surface treatment section exhibits a water immersion action and the second surface treatment section exhibits a water repellency action. In this case, it is preferable to control the wetting rate of the surface-treated water-soluble inorganic compound particles at the initial stage in contact with water.

In other words, since the wetting rate is a factor that affects the dissolution time, even if the heat of dissolving or dispersing the entire processing unit in water is endothermic, if the wetting rate is too high, the core water solubility Dissolution of the inorganic compound proceeds. As a result, when the excessively dissolved water-soluble inorganic compound is exposed to low-temperature water, re-condensation of hydrate crystals may occur, and aggregates may be formed. On the other hand, if the water repellency is excessive and the wetting rate is too slow, the dissolution itself is hindered, and the surface-treated water-soluble inorganic compound particles may remain undissolved.

For the above reasons, it is more preferable that the material has a certain range of wetting rate.

In general, the value of the wetting rate varies depending on the measurement method and the amount of the sample, but in the present invention, when measured by the Pashban method described later in detail, 0.5 g of the surface-treated water-soluble inorganic compound particles is used. Preferably, the wetting rate due to permeation and capillary action is in the range of 100 to 400 minutes, more preferably in the range of 200 to 400 minutes.

The physical properties of the surface-treated water-soluble inorganic compound particles of the present invention are not particularly limited, but the bulk density is usually 0.3 g / cm ³ or more, preferably 0.5 to 1.4 g / cm. ³ , more preferably 0.6 to 1.2 / cm ³ . Bulk density is too small If it is too large, it may be easy to classify it when it is used by mixing with other particles. The average particle size is preferably from 200 to 2000 m, more preferably from 300 to 1500 m. When the average particle size is less than 200 m, the specific surface area is too large, and it may be difficult to obtain the hydration inhibiting effect.On the other hand, when the average particle size is more than 2000 m, the solubility of the surface-treated water-soluble inorganic compound particles themselves is reduced. It may deteriorate. In addition, the angle of repose is 70. Or less, more preferably 50 ° or less. If the angle of repose exceeds 70 °, the handling of particles may deteriorate. The measurement of the bulk density and the average particle diameter is carried out according to the methods described in Examples described later.

The water content in the surface-treated water-soluble inorganic compound particles is preferably 8% by mass or less, more preferably 7% by mass or less, particularly preferably 6% by mass or less, from the viewpoint of preventing solidification (caking) during storage. The water content in the present invention is measured by the heating loss method specified in JIS K3363-1998. Method for producing surface-treated water-soluble inorganic compound particles

Hereinafter, the method for producing the surface-treated water-soluble inorganic compound particles of the present invention will be described in detail. The method for producing surface-treated water-soluble inorganic compound particles of the present invention includes the following first step and second step.

The first step is a step of adding an aqueous solution of a water-soluble polymer compound to the core particles of the water-soluble inorganic compound, and treating the surface of the core particles of the water-soluble inorganic compound with the water-soluble polymer compound. The water-soluble inorganic compound core particles are charged into a granulation and coating apparatus described below, and an aqueous solution of a water-soluble polymer compound is added thereto to perform surface treatment.

In the case of an organic water-soluble polymer compound, the aqueous solution of the water-soluble polymer compound is usually 0.1 to 90% by mass, preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass, and has a viscosity ( (Measured value at 25 ° C using Brookfield viscometer) Force 0.001 to 100 Pa's, preferably 0.0005 to 50 Pa's It is preferable to use a certain organic water-soluble polymer compound aqueous solution. In the case of an inorganic water-soluble polymer compound, it is usually preferably 1 to 60% by mass, preferably 5 to 55% by mass, and more preferably 10 to 50% by mass. It is preferable that the aqueous solution of the water-soluble polymer compound is added dropwise or sprayed to the core particles of the water-soluble inorganic compound in a stirred and fluidized state.

The second step is a step of adding a poorly water-soluble compound to the water-soluble inorganic compound core particles treated in the first step, and subjecting the particles to a surface treatment.

The water-soluble inorganic compound core particles treated in the first step are filled in a granulation / coating apparatus described later, and a water-insoluble compound is added thereto to perform a surface treatment. It is preferable that the hardly water-soluble compound is melted to be in a liquid state, and the liquid is dropped or spray-added to the water-soluble inorganic compound surface-treated in the first step of the stirring / flowing state.

In the above first and second steps, the following methods may be mentioned as specific methods for granulating and coating the water-soluble inorganic compound core particles. (1) A stirring granulation method in which a treating agent (a water-soluble polymer compound, a poorly water-soluble compound) is added to the water-soluble inorganic compound core particles, and the mixture is stirred with a stirring blade to granulate and coat. A tumbling granulation method in which a treating agent is sprayed while the inorganic compound core particles are tumbled to granulate and coat, (3). The treating agent is sprayed while fluidizing the water-soluble inorganic compound core particles. The first step and the second step described above may be performed by the same granulation / coating method and apparatus, or a plurality of granulation / coating methods. The methods and apparatus may be combined. Hereinafter, each method, manufacturing apparatus, conditions and the like will be described.

(1). Agitation granulation method

In the stirring granulation method, any type of stirring granulator can be used. Among them, it is preferable that the apparatus has a stirring shaft provided with a stirring blade at the center of the inside, and has a structure in which a clearance is formed between the stirring blade and the vessel wall when the stirring blade rotates. The clearance is preferably from 1 to 30 mm, more preferably from 3 to 10 mm. If the clearance is less than 1 mm, the mixing machine may be easily overpowered due to the adhesion layer. If it exceeds 30 mm, the compaction efficiency is reduced, so that the particle size distribution becomes broad, and the granulation time becomes longer, which may lower the productivity. Has such a structure Examples of agitating granulators include Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and vertical granule Ichiichi Ichiichi (manufactured by Parek Co., Ltd.). Device. It is particularly preferable to use a horizontal type mixing tank having a stirring shaft at the center of a cylinder and a stirring blade attached to the shaft to mix powder. Such mixers include, for example, a Lödige mixer (manufactured by Matsupo Corporation) and a blow shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.).

Preferred granulation conditions in the stirring granulation method are shown below.

(i) Froude number (Fr number)

In the stirring granulation method, the Froude number defined by the following formula is preferably from 1 to 16, and more preferably from 2 to 9. If the fluid number is less than 1, the surface treatment may be insufficient due to insufficient fluidization. On the other hand, if it exceeds 16, the shearing force on the particles becomes too strong, and the surface treatment may be broken.

F r = V ² / (RX g)

V: Peripheral speed at the tip of the stirring blade (mZ s)

R: Rotation radius of stirring blade (m)

g: Gravitational acceleration (mZ s ² )

(i i) Chopper rotation speed

In the stirring granulation method, the stirring granulator used is equipped with a chopper that rotates at a high speed to promote the compaction of the granules and the disintegration of coarse powder. The rotation speed of the chopper is preferably such that the surface treatment portion is not broken. The tip speed (peripheral speed) of the chopper is preferably 3 OmZs or less, more preferably 0 to 20 mZs or less.

(i i i) Granulation time

In the stirring granulation method, the granulation time in batch granulation and the average residence time in continuous granulation are preferably from 0.5 to 20 minutes, more preferably from 3 to 10 minutes. If the granulation time (average residence time) is less than 0.5 minutes, the time is too short to control the granulation to obtain a suitable average particle diameter and bulk density, and the particle size distribution becomes broad. There is. If it exceeds 20 minutes, the time may be too long and the productivity may decrease.

(iv) Filling rate of water-soluble inorganic compound core particles In the stirring granulation method, the filling rate of the water-soluble inorganic compound core particles into the granulator (the charged amount)

) Is preferably 70% by volume or less of the total internal volume of the mixer, more preferably 15 to 40% by volume. If the filling ratio (prepared amount) exceeds 70% by volume, the mixing efficiency in the mixer will decrease, and granulation may not be performed properly.

(v) Method of adding treatment agent

In the stirring granulation method, a treating agent such as an aqueous solution of a water-soluble polymer compound or a sparingly water-soluble compound is preferably added dropwise or sprayed to particles in a stirred and fluidized state. After dropping or adding a treating agent or the like to the particles in a stationary state, stirring can be started to perform granulation and coating operations. However, in order to enhance the coatability, it is preferable to add the particles by dropping or spraying to the particles in the stirring-fluid state.

(2). Rolling granulation method

In the rolling granulation method, any type of rolling granulator can be used. Among them, a drum-shaped cylinder that rotates to perform processing is preferable, and a thing provided with a baffle plate of an arbitrary shape is particularly preferable. Examples of the drum type granulator include a horizontal cylindrical type granulator, a conical drum type granulator described in the first edition of the first edition of the Granulation Hundred Book, edited by the Japan Powder Industry Association, a multi-stage conical drum type granulator, Drum type granulators with stirring blades and the like can be mentioned. Preferred granulation conditions in the tumbling granulation method are shown below.

(0 processing time

The processing time in the batch system and the average residence time defined by the following formula in the continuous system are preferably from 5 to 120 minutes, more preferably from 10 to 90 minutes, and still more preferably from 10 to 40 minutes. If the time is less than 5 minutes, high bulk density may not be obtained, while if it exceeds 120 minutes, productivity may be reduced or particles may be disintegrated.

Tm = (m / Q) X 60

Tm: Average residence time (min)

m: Particle retention amount in the container rotary mixer (kg)

Q: Capacity in continuous operation (kg / hr)

(ii) Froude number (F r)

It is preferable to select a condition in which the Froude number defined by the following formula is 0.01 to 0.8. The number of fluids is more preferably 0.05 to 0.7, and 0.1 to 0.6. 5 is more preferred. If the Froude number is less than 0.01, uniform and high bulk density particles may not be obtained.On the other hand, if the Froude number is more than 0.8, particles are scattered and normal in the case of a drum type mixer. Shear mixing may not occur.

F r = V ² / '(RXg)

V: Peripheral speed of the outermost periphery of the rotary mixer (mZs)

R: Radius from the center of rotation of the outermost periphery of the rotary mixer (m)

g: Gravitational acceleration (mZ s ² )

(iii) Volume filling rate (X)

It is preferable to select conditions under which the volume filling ratio defined by the following formula is 15 to 50% by volume. The volume filling ratio is more preferably 20 to 45% by volume, and even more preferably 25 to 40% by volume. If the volume filling ratio is less than 15% by volume, productivity may be poor, but if it exceeds 50% by volume, good shear mixing may not occur. Volume filling ratio (X) = (M / p) / VX 100

M: Amount of water-soluble inorganic compound core particles charged to the rotary mixer (g)

P: Bulk density of water-soluble inorganic compound core particles (gZL)

V: Volume of rotating container mixer (L)

(iv) Treatment agent addition method

In the tumbling granulation method, a treating agent such as an aqueous solution of a water-soluble polymer or a poorly water-soluble compound is added by spraying to the particles in a rolling / flowing state. After the treatment agent or the like is dropped or added to the particles in a stationary state, stirring is started to perform granulation and coating operations. However, in order to enhance the coatability, it is preferable to add the particles in a state of being stirred or flowing by dropping or spraying.

(3). Fluidized bed granulation method

In the fluidized-bed granulation method, any type of fluidized-bed granulator composed of a fluidized bed main body, a flow straightening plate, a blower, an intake filter, an air heater, a cooler, a spray device, a dust collector, and the like can be used. For example, batch type fluidized bed granulator (top spray type, side spray type, bottom spray type, etc.) described in Japan Powder Technology Association, Granulation Handbook 1st edition, 1st printing, spouted fluidized bed granulator, Spouted bed granulator, semi-continuous Fluidized bed granulator (dispersed plate inverted discharge type, bottom discharge type, side wall discharge type, etc.) Continuous fluidized bed granulator (horizontal multi-chamber type, cylindrical type, etc.) can be suitably used. Examples of the use of specific equipment are the batch type fluidized bed granulator G 1 att-I P OWR EX series [manufactured by Baurex Co., Ltd.], Floco Ichiyuichi series [manufactured by Okawara Seisakusho Co., Ltd.], continuous flow The MIXGR AD series of bed granulators [manufactured by Okawara Seisakusho Co., Ltd.] and the like.

As the granulation conditions in the fluidized bed granulation method, the average thickness of the raw material powder layer at the time of standing is preferably about 50 to 500 mm. After that, air is sent to the fluidized bed to make the powder fluidized, and then spraying of a treating agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is started. As the spray nozzle, it is also preferable to use a two-fluid nozzle in order to improve the spray state, in addition to a normal pressurizing nozzle. The average droplet diameter at this time is preferably about 5 to 500 m. As spraying progresses, granulation proceeds and the particle size increases, so granulation is performed while adjusting the wind speed to maintain a fluidized state. The wind speed is adjusted in the range of 0.2 to 4. O m / s, and the wind temperature is adjusted to 5 to 70 ° C, preferably 7 to 65 ^. It is preferable to perform the production while periodically dropping the fine particles attached to the bag filter with pulsed air.

In the case where the surface-treated water-soluble inorganic compound particles are produced by the method for producing the surface-treated water-soluble inorganic compound particles, the temperature of the surface-treated water-soluble inorganic compound particles immediately after the completion of the second step is preferably equal to or higher than the melting point of the anionic surfactant acid precursor. In particular, when adding the poorly water-soluble compound in the second step, it is good to pay attention to the temperature of the water-soluble inorganic compound core particles treated in the first step. Specifically, it is preferable that the temperature of the particles be equal to or higher than the melting point of the poorly water-soluble compound. When adding the poorly water-soluble compound, if the temperature of the water-soluble inorganic compound core particles treated in the first step is lower than the melting point of the poorly water-soluble compound, the surface after the surface treatment with the poorly water-soluble compound is completed. The temperature of the treated water-soluble inorganic compound particles is preferably equal to or higher than the melting point of the poorly water-soluble compound. If the temperature is lower than the melting point, the dispersibility and uniformity of the poorly water-soluble compound in the granulation-coating system will be poor, and the surface treatment with the poorly water-soluble compound may be insufficient.

The surface-treated water-soluble inorganic compound particles obtained by the above method may be further surface-treated with an organic or inorganic fine powder. Surface treatment The water-soluble inorganic compound particles Examples of the fine powder to be treated include a surfactant at room temperature, a long-chain fatty acid salt, an aluminosilicate, an oil-absorbing carrier, and a clay mineral.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Long-chain fatty acid salts include alkali and non-alkali metal long-chain fatty acid salts, aluminosilicates such as A-type, P-type, X-type, etc., and oil-absorbing carriers such as silica, silicate compounds, and spherical porous hydrous amorphous Examples of clay minerals such as silicic acid include montmorillonite, nontronite, paiderite, pyrophyllite, savonite, hectorite, stevensite, and talc. These can be used alone or in an appropriate combination of two or more. Of these, long-chain fatty acid salts of non-alkali metals, talc, and aluminoketes are preferred. Non-alkali metal long-chain fatty acid salts and luk are water-repellent, preventing aggregation of water-soluble inorganic compounds.Aluminosilicates are commonly used as Ca-trapping builder, and when used alone for surface treatment, mixed Acts as a treating agent on the surface of the detergent particles to be produced.

The fine particles preferably have a primary particle diameter of 1 Z5 or less, more preferably 1 Z10 or less, based on the average particle diameter of the surface-treated water-soluble inorganic compound particles. The amount of the fine powder is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the surface-treated water-soluble inorganic compound particles.

The surface-treated water-soluble inorganic compound particles obtained by the above-described method can be classified as necessary to use only the surface-treated water-soluble inorganic compound particles having a desired particle size. As the classification device, any generally known classification device can be used, and particularly, a sieve can be suitably used. Among them, gyroscopic sieves, flat sieves and vibrating sieves are preferred. The gyro sieve is a sieve that gives a horizontal circular motion to a slightly inclined plane sieve. A flat sieve is a sieve that gives a reciprocating motion almost parallel to the surface on a slightly inclined flat sieve. A vibrating sieve is a sieve that vibrates rapidly in a direction substantially perpendicular to the sieve surface. The time of sieving is preferably 5 seconds or more, and it is also preferable to use a tapping pole to improve sieving efficiency. Specific examples of such a sieve include Gyro Shifu Yuichi (manufactured by Tokuju Kosakusho Co., Ltd.), Rottekus Screener (manufactured by Seishin Enterprise), and Dalton Vibrating Sieve (manufactured by Dalton Co., Ltd.). Can be Vibration by the sieve is suitably 60 to 300 times / minute, preferably 100 to 250 times / minute, More preferably, it is given by a vibration of 150 to 2000 times / minute. If the frequency of the sieve is less than 60 times the Z-minute, the classification effect may be deteriorated, while if it exceeds 300 times, dust generation may increase.

Of the surface-treated water-soluble inorganic compound particles separated in the classification step, it is preferable that the fine powder is again put into the granulator together with the water-soluble inorganic compound core particles, and the granulation is preferably performed for the coating operation. Also, the coarse powder is pulverized to a particle size equivalent to that of the water-soluble inorganic compound before the granulation / coating operation, and then again put together with the core particles of the water-soluble inorganic compound into the granulator, where the granulation / coating operation is performed. It is preferable to subject to. At this time, as a crusher for crushing coarse powder, a model having a classification screen and a rotary blade is preferable. Examples of such a mill include Fitzmill (manufactured by Hosokawa Micron Corp.), New Speed Mill (manufactured by Okada Seie Co., Ltd.), and Feather Mill (manufactured by Hosokawa Micron Corp.). In addition, it is also possible to pulverize while cooling by flowing cold air through the pulverizer. It is also possible to classify the cold air and the ground product with a cyclone and then classify the fine powder. Furthermore, the particle size distribution becomes sharper by multi-stage grinding. The peripheral speed of the tip of the blade of the mill is preferably 15 to 9 OmZs, more preferably 20 to 8 OmZs, and even more preferably 25 to 7 OmZs. If the tip peripheral speed is less than 15 mZ s, the crushing ability may be insufficient, and if it exceeds 9 O mZ s, the crushing may be liable to occur.

In order to make the surface-treated water-soluble inorganic compound particles have a high bulk density and a small angle of repose, after the surface treatment in the first step and the second step, the third step: the water solubility after the surface treatment in the second step It is preferable to include a step of suppressing hydration crystal growth on the surface of the inorganic compound core particles. Thereby, it is preferable to maintain the smoothness of the surface shape of the surface-treated water-soluble inorganic compound particles. When the hydrated crystal grows, many irregularities are generated on the surface of the core particles of the water-soluble inorganic compound, the bulk density decreases, and the angle of repose increases. In some cases, the hydrated crystals break through the surface treatment and solidify with the hydrated crystals protruding from nearby surface-treated water-soluble inorganic compound particles, resulting in strong hydrated consolidation.

Methods for suppressing hydrated crystals include [1] a method of cooling the surface-treated particles after the second step, and [2] a method of drying the surface-treated particles after the second step. You. Among them, [1] Cooling method is preferred from the viewpoint of maintaining good solubility. [1] The method of cooling the surface-treated particles after the second step is not particularly limited as long as the surface-treated water-soluble inorganic compound particles can be cooled to 30 ° C or lower, preferably 25 or lower. The cooling rate is preferably 5 ° C hr or more, more preferably 10 ° C hr or more. The cooling method and device are not particularly limited, but the cooling device is classified into a cooling device using a cooled heat transfer surface and a cooling device using an air flow. For example, a torus disk (manufactured by Hosoka Micron Corp.), Frigomix (manufactured by Nisshin Engineering Co., Ltd.), etc., may be used as those using a cooled transmission surface. Fluidized beds can be used for cooling by using airflow. Specific examples of the use of the apparatus are the batch type fluidized bed granulator G 1 att-POWR EX series (manufactured by Baurex), Floco Ichiyuichi series (manufactured by Okawara Corporation), continuous flow The MI XGRAD series of bed granulators (manufactured by Okawara Seisakusho Co., Ltd.) and the like. In view of the possibility that the surface-treated portion of the surface-treated water-soluble inorganic compound particles may be peeled off or broken, it is preferable to use a fluidized bed.

[2] The method of drying the surface-treated particles after the second step is not particularly limited as long as the surface-treated water-soluble inorganic compound particles can be dried. More specifically, a similar device used in the above method [1] can be used as a drying device by setting the temperature of a heating medium such as a transmission surface or an airflow to 50 to 300 ° C, preferably 60 to 250 ° C. Utilizing and drying. Granular detergent composition

The surface-treated water-soluble inorganic compound particles obtained by the above production method can be used as they are as a granular detergent composition.However, they should be mixed with a detergent particle group as an alkaline agent to form a granular detergent composition. Is preferred. This group of detergent particles is usually selected from surfactant-containing particles containing a surfactant and an inorganic compound, enzyme particles, bleach particles, and bleach activator particles. The mixing ratio (mass ratio) is preferably 3/97 to 97/3, more preferably 5/95 to 95/5, and still more preferably 10/90 to 90/10. preferable.

The granular detergent composition may optionally include surface-treated water-soluble inorganic compound particles and a detergent particle group. Can be obtained by mixing. As the mixing method, dry mixing is preferably used. As the mixer to be used, any mixer may be used as long as various kinds of particles can be sufficiently mixed. As the mixing machine, a mixing machine of a horizontal cylindrical type, a double cone type, a V type, a rotation type and a revolution type can be suitably used. Further, a stirring granulator or a tumbling granulator may be used. Preferably, a horizontal cylindrical type or a double conical type is used, at a temperature of 0 to 50 ° C,? 1 "is mixed in the order of 0.01 to 0.2 (calculation formula is as described above). At this time, the order of adding various particles and other components is not particularly limited.

The granular detergent composition preferably contains (a) the above-mentioned surface-treated water-soluble inorganic compound particles, and (b) surfactant-containing particles containing a surfactant and an inorganic compound. In order to prevent the classification of the granular detergent composition in the container, the ratio (al) / bl) of the average particle diameter of the (al) surface-treated water-soluble inorganic compound particles and the (bl) surfactant-containing particles is preferably Is from 0.5 to 2, more preferably from 0.5 to 1.5, and even more preferably from 0.6 to 1.3. The ratio (a 2) / (b 2) of the bulk density of (a 2) the surface-treated surface-treated water-soluble inorganic compound particles to (b 2) the surfactant-containing particles is preferably 0.5 to 2 , More preferably 0.6 to 1.5, and still more preferably 0.6 to 1.4.

(a) The blending amount of the surface-treated water-soluble inorganic compound particles in the granular detergent composition is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. . On the other hand, the blending amount of the surfactant-containing particles in the granular detergent composition is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and still more preferably 50 to 90% by mass. .

The mixing ratio of (a) the surface-treated water-soluble inorganic compound particles and (b) the surfactant-containing particles is (a) particle Z (b) particles (mass ratio), preferably 1Z99 to 50Z50, more preferably 5/50. It is 95-40 / 60, particularly preferably 10 / 90-30 / 70. If the mass ratio exceeds 50/50, fluidity and solubility may be significantly deteriorated.

(b) The surfactant-containing particles contain a surfactant and an inorganic compound. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more. It can be used together.

The anion surfactant is not particularly limited as long as it is conventionally used in detergents, and various anion surfactants can be used. For example, the following can be mentioned.

(1) Linear or branched alkylbenzene sulfonate having 8 to 18 carbon atoms (LAS)

(2) C10-C20 alkyl sulfate (AS) or alkenyl sulfate

(3) Hyorefin sulfonate (AOS) having 10 to 20 carbon atoms

(4) Alkane sulfonate having 10 to 20 carbon atoms

(5) Ethylene oxide, propylene oxide, butylene oxide or a mixture thereof, having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 mol or less. Alkyl ether sulfate (AES) or alkenyl ether sulfate with

(6) Ethylene oxide, propylene oxide, butylene oxide or the like having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 mol or less. Alkyl carboxylate or alkenyl ether carboxylate to which a mixture of

(7) alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms

(8) Higher fatty acid salts having 10 to 20 carbon atoms

(9) Saturated or unsaturated α-sulfofatty acid (α-SF) salt having 8 to 20 carbon atoms or its methyl, ethyl or propyl ester, etc.

Examples of anionic surfactants include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (eg, sodium or potassium salts), alkali metal salts of AOS, SF, and AES (eg, sodium or potassium salts) And alkali metal salts of higher fatty acids (eg, sodium or potassium salts).

Examples of the nonionic surfactant include the following. (1) An alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, preferably 3 to 30 mol, preferably 5 to 20 mol. Polyoxyalkylene alkyl (or alkenyl) ether

Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferred. The aliphatic alcohol used here includes a primary alcohol and a secondary alcohol. Further, the alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferred.

(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether

(3) Alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester, for example, a fatty acid alkyl ester alkoxylate represented by the following general formula (I)

R ^ O (OA) _n OR ² … (I)

(Wherein, RiCO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. And n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ² has a substituent having 1 to 3 carbon atoms. May represent a lower (C1-4) alkyl group.)

(4) Polyoxyethylene sorbitan fatty acid ester

(5) Polyoxyethylene sorbite fatty acid ester

(6) Polyoxyethylene fatty acid ester

(7) Polyoxyethylene hydrogenated castor oil

(8) Glycerin fatty acid ester

Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 50 or less and an HLB of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers, fatty acid methyl esters, and ethylene oxide Fatty acid methyl ester ethoxylate to which side is added, fatty acid methyl ester ethoxypropoxylate to which ethylene oxide and propylene oxide are added to fatty acid methyl ester, and the like are preferably used. These nonionic surfactants may be used alone or in combination of two or more. be able to.

The HLB of the nonionic surfactant in the present invention is a value obtained by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka co-edited, "New Edition Surfactant Handpuck", Industrial Books Co., Ltd., 1991, p. 234).

In addition, the melting point in the present invention is a value measured by a melting point measuring method described in JISK 0064-1992 "Method for measuring melting point and melting range of chemical products" As the cationic surfactant, for example, Can be mentioned.

(1) Di long chain alkyl di short chain alkyl type quaternary ammonium salt

(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt

(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt

(The long-chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and the short-chain alkyl is an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, and 2 to 4 carbon atoms. Represents a 2-3 hydroxyalkyl group or a polyoxyalkylene group.)

Examples of the amphoteric surfactant include an amphoteric surfactant such as an imidazoline-based or amido-bein-in-based surfactant.

(b) The surfactant in the surfactant-containing particles is preferably an anion surfactant and a nonion surfactant from the viewpoint of cleaning performance, and a combination use of an anion surfactant and a nonion surfactant. Is more preferred. When the anionic surfactant and the nonionic surfactant are used together, the mass ratio of the compounding amounts of the anionic surfactant and the nonionic surfactant (anionic surfactant Z nonionic surfactant) is 0.1 to 10%. Is preferred, 0.2 to 8 is more preferred, and 0.3 to 7 is even more preferred.

The amount of the surfactant is preferably (10) 50 to 50% by mass in the surfactant-containing particles (a) from the viewpoint of solubility and fluidity due to mixing with the surface-treated water-soluble inorganic compound particles. More preferably, it is 15 to 40% by mass. If the amount is more than 50% by mass, the fluidity may be deteriorated. If the amount is less than 10% by mass, the solubility may be deteriorated.

(b) The surfactant-containing particles further contain an inorganic compound. This allows for liquidity The effect of improvement is obtained. The inorganic compound is not particularly limited, but all inorganic compounds contained in the following inorganic builders, reducing agents, and extenders can be used.

, Can be used alone or in combination of two or more. Among them, as the inorganic compound, sodium carbonate, potassium carbonate, sodium sulfate, and aluminosilicate are preferable.

(b) The compounding amount of the inorganic compound in the surfactant-containing particles is 10 to 80% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. If the amount of the inorganic compound is too small, the fluidity may be degraded. If the amount is too large, dusting of the powder may occur.

(b) The surfactant-containing particles preferably further contain a water-soluble polymer compound, whereby the fluidity and solidification after storage over time can be further improved. Examples of the water-soluble polymer compound include the same water-soluble polymer compounds as those described above in (a) the surface-treated water-soluble inorganic compound particles. The water-soluble polymer compound used here may be the same as or different from (a) the water-soluble polymer compound. (B) As the water-soluble polymer compound in the surfactant-containing particles, an acrylic acid polymer compound or a cellulose polymer compound is preferable, and as the acrylic polymer compound, an acrylic acid polymer, acrylic acid / Maleic acid copolymers are preferred. As the cellulosic polymer compound, carboxymethyl cellulose (CMC) is preferable. The weight average molecular weight of the water-soluble polymer compound is preferably from 1,000 to 1,000,000. The water-soluble polymer compound can be used alone or in an appropriate combination of two or more.

(b) The compounding amount of the water-soluble polymer compound in the surfactant-containing particles is 0.1 to 10% by mass, preferably 0.5% to 9% by mass, and more preferably 1 to 8% by mass. . If the amount of the water-soluble polymer compound is too small, the intended effect may not be obtained. If the amount is too large, the solubility of (b) the surfactant-containing particles themselves may be deteriorated.

The surfactant-containing particles (b) of the present invention may contain the following optional components in addition to the above essential components. Although the inorganic compound is an essential component, it will be described in more detail below. Water-soluble polymer compounds are also described redundantly. Each of these optional components can be used alone or in combination of two or more.

(1) Cleaning builder

(b) Examples of the washing builder to be incorporated into the surfactant-containing particles include inorganic and organic builders.

(1-1) Inorganic builder

Examples of the inorganic builder include sodium salt, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, amorphous layered sodium silicate, and the like, sulfuric acid, and the like. Neutral salts such as sodium, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytates, the following general formula (II) X ¹ (M ₂₀ ) · A 1 ₂ 〇 ₃ · y ¹ (S i〇 ₂ ) · w ¹ (H ₂ 〇) (II)

(Wherein, M is an alkali metal atom such as sodium, potassium, etc., X ¹ , y ^1, and w ¹ indicate the number of moles of each component, and generally, X ¹ is 0.7 to 1.5, y ¹ the number of 0. 8~6, w ¹ represents any positive number.)

A crystalline aluminosilicate represented by the following general formulas (1 1 1) and (IV)

^{_{X 2 (M 2 0) ·}} A 1 2 0 3 · y 2 (S i 0 2) - w 2 (H 2 0) (III) ( wherein, M is sodium, an alkali metal atom such as potassium, x ² , Y ² and w ² represent the number of moles of each component, and generally, X ² is 0.7 to 1.2, y ² is 1.6 to 2.8, w ² is 0 or any positive number. Indicate the number.)

^{_{X 3 (M 2 0) ·}} A 1 2 0 3 · Y 3 (S i 0 2) - z 3 (P 2 0 5) - w 3 (H 2 0)

(I V)

(Wherein, M is an alkali metal atom such as sodium or potassium, x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, and generally, X ³ is 0.2 to 1.1. , y ³ from 0.2 to 4.0, 2 ³ 0. 001-0. 8, w ³ 0 or amorphous aluminosilicates and the like represented by any showing a positive number.) can be mentioned. Among the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, and sodium aluminum silicate are preferred.

(1 -2) Organic builder Examples of the organic builder include aminocarboxylic acid salts such as triacetate triacetate, ethylenediaminetetraacetate, i3-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate Hydroxyamino carboxylates such as hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxysethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate and dalconate Cyclocarboxylates such as pyromellitate, benzopolycarboxylate, and cyclopentanetetracarboxylate; carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid Ethers such as mono or disuccinate Rubonates; polymers or copolymers such as itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, and aspartic acid; polysaccharide oxides such as starch, cellulose, amylose, and pectin; And polysaccharides such as oxymethylcellulose.

Among these organic builders, preferred are citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylate-maleic acid copolymer, and polyacetalcarboxylate, and particularly, hydroxyiminodisuccinate. A salt of an acrylic acid-maleic acid copolymer having a weight average molecular weight of 1,000 to 80,000, a polyacrylic acid salt and a weight average molecular weight of 800 to 1,000,000 described in JP-A-54-52196. Suitable are polyacetone carponic acid salts such as 5,000, preferably 5,000 to 200,000 polyglyoxylic acid.

The blending amount of the organic builder is preferably 0.5 to 20% by mass, more preferably 1 to 0% by mass in the surfactant-containing particles.

Also, for the purpose of improving detergency and dispersibility of stains in washing liquid, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, atalylic acid-maleic acid copolymer, polyaceta It is preferable to use an organic builder such as a monocarboxylate and an inorganic builder such as zeolite in combination.

(2) Dissolution promoter

(b) Examples of the dissolution promoter to be incorporated into the surfactant-containing particles include, for example, inorganic ammonium salts such as potassium carbonate, ammonium sulfate, and ammonium chloride; Sodium monobenzenesulfonate, sodium xylenesulfonate, sodium benzenesulfonate having 1 to 5 carbon atoms such as sodium cumene sulfonate, sodium benzoate, sodium benzenesulfonate, sodium chloride, citric acid, D- Examples include water-soluble substances such as glucose, urea, and sucrose.

Of these, potassium carbonate and sodium chloride are preferable, and carbon dioxide rim is particularly preferable in view of the balance between the solubility improving effect and the cost.

When potassium carbonate is blended, the blending amount is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, more preferably 2 to 12% by mass in the surfactant-containing particles from the viewpoint of the solubility improving effect. It is 5 to 10% by mass.

When sodium chloride is compounded, the amount of the compound should be as follows: (b)

) In the surfactant-containing particles, it is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 3 to 7% by mass.

(3) Swellable water-insoluble substance

(b) Examples of the swellable water-insoluble substance to be incorporated in the surfactant-containing particles include powdered cellulose, crystalline cellulose, bentonite, and the like.

(4) Fluorescent agent: bis (triazinylaminostilbene) disulfonic acid derivative (Tinopal AMS—GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X], etc.

(5) Antistatic agent: cationic surfactant such as dialkyl-type quaternary ammonium salt

(6) Anti-redeposition agent: Cellulose derivatives such as carboxymethylcellulose

(7) Extender: sodium sulfate, potassium sulfate, etc.

(8) Reducing agent: sodium sulfite, potassium sulfite, etc.

(9) Fragrance

(10) Dye

(11) Bleaching activation catalyst

Bleaching activation catalysts include transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum, and nitrogen atoms and oxygen. A complex is formed via an atom or the like, and the transition metal contained is preferably cobalt, manganese, or the like. Particularly, manganese is preferred.

(b) The average particle size of the surfactant-containing particles is preferably from 200 to 150001, more preferably from 250 to 1000 rn, even more preferably from 300 to 700 m. The bulk density is preferably 0. 4~1. 2gZcm ^3, more preferably ^{0. 5~1. 0 gZ cm 3} . The average particle diameter and the bulk density are measured according to the methods described in Examples.

(b) The water content of the surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and still more preferably 5 to 8% by mass from the viewpoint of solubility and storage stability.

(b) The surfactant-containing particles can be obtained by the following granulation method. An extruding granulation method in which the raw material powder and one component of the binder (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, and then extruded and granulated. Kneading. Kneading, crushing and granulating methods to crush and granulate, stirring granulation method in which a binder component is added to raw material powder and agitating with stirring blades to granulate, spraying one component of binder while rolling raw material powder And a fluidized bed granulation method in which a raw material powder is fluidized while a liquid binder is sprayed and granulated. Specific equipment and conditions that can be used in these granulation methods are described in JP-A-2003-105400, JP-A-2003-238998, edited by the Japan Powder Technology Association and the first edition of the Granulation Handbook. It is as follows.

The granular detergent composition of the present invention comprises, from the viewpoint of preventing solidification (caking) during storage, one of (a) the surface-treated water-soluble inorganic compound particles and (b) the surfactant-containing particles, and preferably both of them. It is preferable to perform a surface treatment with an organic or inorganic fine powder. The fine powder is not particularly limited as long as it is a fine powder having a primary particle diameter of 30 m or less, preferably 0.1 to 10 m. Examples of the fine powder include a room temperature solid surfactant, a long-chain fatty acid alkaline earth, and the like. Examples include metal salts, aluminosilicates, silica, clay minerals, and the like. Of these, aluminosilicates are preferred.

When (a) particles and / or (b) particles are surface-treated with fine powder, the amount of the fine powder is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass in the granular detergent composition. %, More preferably 0.5 to 3% by mass. The water content of the granular detergent composition of the present invention is preferably 10% by mass or less, more preferably 4 to 9% by mass, and still more preferably 5 to 8% by mass from the viewpoint of solubility and storage stability.

/ 6

In the present invention, a combination of (a) a surface-treated water-soluble inorganic compound particle and (b) a surfactant-containing particle that particularly satisfies the following conditions is preferable.

(a) The water-soluble inorganic compound of the particles is sodium carbonate or potassium carbonate, and the water-soluble polymer compound is one or two selected from a vinyl polymer compound, a polysaccharide or a derivative thereof, and a polyester polymer compound. (A) the amount of the poorly water-soluble compound in the particles is less than 10% by mass, and (b) the amount of the surfactant in the surfactant-containing particles is 10 to 50% by mass.

The granular detergent composition of the present invention contains, in addition to (a) surface-treated water-soluble inorganic compound particles and (b) surfactant-containing particles, other particles such as enzyme particles, bleach particles, and bleach activator particles. be able to.

(1) Enzyme particles

As the enzyme in the enzyme particles, commercially available enzyme particles currently used for granular clothing detergents can be used as they are. Specifically, proteases such as sabinase 12T, kannase 12Τ, 24Τ, evarase 8T, Deozyme, lipases such as revorase ultra 50T, LIΡΕΧ50Τ, etc., amylase such as Termamyl 100, etc., cellzym 0 Cellulase of 7Τ and others (above, manufactured by Nopozymes), Maxacal 45G, Maxam 30G, Properase 1000E (above, manufactured by Diene Core) and the like.

The average particle size of the enzyme particles is preferably from 200 to 1000 m, more preferably from 300 to 700 m, from the viewpoint of solubility and storage stability. The measurement of the average particle diameter is based on the measuring method described in Examples described later.

The amount of the enzyme particles is preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, based on the total amount of the granular detergent composition, from the viewpoint of cleaning performance.

(2) Bleach particles

Bleach particles consist of hydrogen peroxide or a peroxide that generates hydrogen peroxide when dissolved in water, usually one of sodium percarbonate and sodium perborate Or both are used. In particular, sodium percarbonate is preferred from the viewpoint of stability over time. These peroxides are treated with a coating or the like in order to prevent decomposition due to contact of water or other detergent components with the surfaces of the particles composed of the peroxide. Used in Various oxygen bleaching agents in the form of particles subjected to coagulation have been proposed, and examples thereof include bleaching agent particles described in Japanese Patent No. 2918991. The bleaching agent particles are granulated products obtained by separately spraying an aqueous boric acid solution and an aqueous solution of an alkali metal silicate onto particles of sodium percarbonate kept in a fluid state, and drying. In addition to the above, a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent. The average particle diameter of the coated sodium percarbonate particles is preferably from 100 to 200 m, more preferably from 200 to L 00, from the viewpoint of stability and solubility of the sodium percarbonate particles. 0 im, more preferably 300 to 800 m, such as SPC-D manufactured by Mitsubishi Gas Chemical Co., Ltd. The blending amount of the bleaching particles depends on the bleaching performance and efficiency. Therefore, it is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the granular detergent composition. (3) Bleaching activator particles

The bleaching activator in the bleaching activator particles may be tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzoic acid having 8 to 12 carbon atoms, or a mixture thereof. Salts are preferred. Of these, 4-decanoyloxybenzoic acid, sodium 4-dodecanolyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred. Xybenzoic acid and sodium 4-nonanoyloxybenzenesulfonate are more preferred.

The bleach activator is obtained by heating and melting a solid binder material at room temperature, such as polyethylene glycol of PEG # 300 to # 200, preferably PEG # 400 to # 600. After dispersing a bleach activator and powder of surfactant such as olefin sulfonate, alkylbenzene sulfonate, alkyl sulfate, etc., extrude it and extrude noodle-like bleach activator granules of about 1 mm in diameter It is preferable to mix the product after lightly pulverizing it to a length of about 0.5 to 3 mm. Surfactant powder Preferred is a <<-olefin sulfonic acid salt having an alkyl chain length of 14.

The blending amount of the bleach activator in the granulated product is preferably 30 to 95% by mass, and more preferably 50 to 90% by mass. If the compounding amount is outside this range, it may be difficult to sufficiently obtain the effect of granulation.

The compounding amount of the binder substance is 0.5 to 30% by mass, preferably 1 to 20% by mass, more preferably 5 to 20% by mass in the granulated material. The compounding amount of the surfactant powder is It is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, particularly preferably 5 to 30% by mass in the granulated product.

The average particle size of the bleach activator particles is preferably from 200 to 1500 m, more preferably from 300 to L000 m, from the viewpoint of solubility and storage stability.

The blending amount of the bleach activator particles is preferably from 0.1 to 15% by mass, particularly preferably from 0.3 to 10% by mass, based on the total amount of the granular detergent composition.

(a) Surface-treated water-soluble inorganic compound particles, (b) Surfactant-containing particles, enzyme particles, bleach particles, bleach activator particles, etc. can be used after the surface is colored with a dye or pigment. . At this time, dyes and pigments used for coloring should not cause dyeing on clothes during washing. Examples of such dyes and pigments include ultramarine, koranildarine CG-130 (CI Nampa 1: 74260), food color red No. 102, acid dye Acid Yellow 141 and the like. These dyes and pigments are converted into an aqueous solution or dispersion, and then the particles are stirred and tumbled in a stirring granulator or a tumbling granulator similar to a granulator for surfactant-containing particles. While adding, it can be colored. In addition, the particles may be colored by spraying the aqueous solution or dispersion liquid onto the particles while the particles are transported on a belt conveyor. The coloring amount is preferably 0.001 to 1% by mass based on the particles to be colored.

In addition, the fragrance may be added to one or both of (a) the surface-treated water-soluble inorganic compound particles and (b) the surfactant-containing particles, and then the respective particles may be mixed. After mixing the water-soluble inorganic compound particles and the (b) surfactant-containing particles, fragrance may be applied. As the fragrance used, the components described in JP-A-2002-146399 and JP-A-2003-89800 can be used. The fragrance is a mixture of a fragrance component, a solvent, a fragrance stabilizer and the like. Granular detergent of the present invention In the composition, the amount of the perfume is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example. The physical properties of the granular detergent composition of the present invention are not particularly limited, but the bulk density is usually 0.3 g / cm ³ or more, preferably 0.5 to: L. 2 g, 'cm ³ And more preferably 0.6 to 1.1 gZcm ³ . The average particle size is preferably from 200 to 1500 m, more preferably from 250 to 1000 m, and even more preferably from 280 to 700 m. If the average particle size is less than 200 m, dust may be easily generated or the handling property may be deteriorated.On the other hand, if the average particle size exceeds 1500 m, it may be difficult to obtain the solubility intended by the present invention. . Further, the fluidity of the granular detergent composition is preferably 60 ° or less, particularly preferably 50 ° or less as a repose angle. In addition, after storage (for example, when stored in a highly permeable container such as a paper container for a long period of time), the fluidity should preferably be 60 ° or less, more preferably 50 ° or less, as the angle of repose. Preferred from the point.

The granular detergent composition of the present invention can be filled into a suitable container to form a granular detergent article in a container. As the material of the container, saving permeability in terms of stability humidity 30 gZm ² • 24 hours preferably (40 ° C, 90% RH ) or less, 25 gZm ² · 24 hours (40 ° C, 90% RH ) or less Is more preferred. These can be achieved by combining general packaging materials and changing the thickness. The moisture permeability in the present invention is JIS

It is measured by the method specified in Z 0208-1976.

The granular detergent composition of the present invention can be further used as a compression detergent such as a tablet detergent and a briguet detergent by compression molding after further mixing a disintegrant and the like. Since the granular detergent composition of the present invention can improve the fluidity and solidification after long-term storage while ensuring sufficient low-temperature solubility, it is particularly suitable for washing in a short-time washing course, and washing in a weak-flow course. It is suitable for applications or purposes, such as for washing, cold water washing, and washing machines with detergent inlets. Washing method

In the washing method of the present invention, the water-soluble inorganic compound particles are surface-treated with an organic or inorganic water-soluble polymer compound, and the treated surface is not treated with a poorly water-soluble compound. Washing the laundry with the surface-treated water-soluble inorganic compound particles at a bath ratio of 7 to 15 LZ kg, preferably 8 to 15 LZ kg, more preferably 10 to 13 L / kg. The washing method is performed at a rinsing temperature of 5 to 12 ° C, preferably 7 to 12 ° C, and more preferably 10 to 12 ° C. According to the present invention, when the washing is performed at the bath ratio and the washing temperature in the above range, the effect of not forming aggregates even when moistened at a low water temperature and a low stirring force is exhibited. Surface that does not form agglomerates even when wet under agitation, exhibits excellent solubility during washing, has excellent fluidity, and prevents adhesion to granulators during manufacturing The treated water-soluble inorganic compound particles, which are blended with the particles, can provide a powdery detergent composition having excellent fluidity and non-solidification properties after long-term storage.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, in the following examples, unless otherwise specified, the composition is “%” by mass%, and the amount of each component in the table is (a) surface-treated water-soluble inorganic compound particles in Tables 1 to 4 and ( b) Regarding the composition of the surfactant-containing particles, the compounding amount as a pure component is shown, and other tables show the compounding amounts of the listed components. Examples and comparative examples

[Examples a1 to a28, Comparative examples a29 to a35]

Method for producing surface-treated water-soluble inorganic compound particles 1 (stirring granulation 1)

1st step

Among the components shown in Tables 1 to 4 below, a water-soluble inorganic compound core particle is equipped with a plow-blade shovel, and the clearance between the shovel and the wall is 5 mm. Then, stirring at a spindle speed of 150 rpm was started (chopper rotation speed: 115 rpm, blade tip speed (peripheral speed): 6.9 m / s). 10 seconds after the start of stirring, an aqueous solution of a water-soluble polymer compound (concentration is described in the raw material column described below, the same applies hereinafter) was spray-added for 180 seconds using a pressurized nozzle (flat nozzle) with a spray angle of 115 degrees. The granulation and coating operations were performed, and the aqueous solution of the water-soluble polymer compound was stored for 10 days at the temperatures shown in Tables 1 to 4 before use. If the water content relative to the total amount of the prepared particles exceeded 10%, the device was dried by introducing hot air into the above device, and the water content was adjusted to the values shown in Tables 1 to 4.

2nd step

The coating operation was carried out by spraying the poorly water-soluble compounds shown in Tables 1 to 4 with a spray nozzle with a spray angle of 60 ° (full cone nozzle) for 180 seconds while continuing to stir with a professional mixer. . Finally, fine powder was added as needed, and stirring was continued for 30 seconds to obtain particles. The coating operation was performed by appropriately passing warm water through the mixer jacket through the first and second steps so that the particle temperature immediately after the completion of the coating operation was as shown in Tables:! To 4.

3rd step

Next, the obtained particles are filled in a fluidized bed (G 1 att-POWREX, model number FD-WRT-20, manufactured by Parex Co., Ltd.), and after filling, air (air) at 15 ° C is filled in the fluidized bed. And cooled the particles to obtain particles cooled to 20 ° C. The wind speed in the fluidized bed was adjusted in the range of 0.2 to 10. Om / s while checking the fluidized state. The obtained particles are classified using a sieve with an aperture of 2000 m, and the surface-treated water-soluble inorganic compound particles that pass through a sieve with an aperture of 2000 m (the average particle diameter, angle of repose, and bulk density are described in Tables 1 to 4. ) Got. Method for producing surface-treated water-soluble inorganic compound particles 2 (stirring granulation 2)

1st step

Of the components shown in Tables 1 to 4 below, 10 L of water-soluble inorganic compound core particles corresponding to a volume of 10 L were charged into a Folberg mixer (F-20, manufactured by Nippon Pneumatic Industries, Ltd.) (filling rate: 50%). (Volume%), paddle peripheral speed 1.4 Agitation was started at 4HLS (chopper stopped). Five seconds after the start of stirring, a water-soluble polymer aqueous solution was spray-added at 100 gZmin using a two-fluid hollow cone nozzle with a spray angle of 70 °, and granulation and coating operations were performed.

2nd step

Bow I Inject the water-insoluble compounds shown in Tables 1-4 at 100 gZmin using the same two-fluid holo-cone nozzle while continuing the stirring operation of the Folberg mixer. A fog was added and a coating operation was performed. Finally, if necessary, fine powder was added, and stirring was continued for 30 seconds to obtain particles.

3rd step

After the completion of the second step, the surface-treated water-soluble inorganic compound particles (the average particle diameter, the angle of repose, and the bulk density are determined in the same manner as in step 3 of the above-described method 1 for producing the surface-treated water-soluble inorganic compound particles). 1-4) were obtained. Method for producing surface-treated water-soluble inorganic compound particles 3 (rolling granulation)

1st step

Of the composition components shown in Tables 1 to 4 below, the water-soluble inorganic compound core particles were mixed with a horizontal cylindrical tumbling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, container: 131.7 L). (With two baffles with a clearance of 20 mm and a height of 45 mm) (filling rate: 20% by volume), and the rolling operation was started at a rotation speed of 22 rpm. Thirty seconds after the start of rolling, a water-soluble polymer aqueous solution was spray-added at 100 gZmin using a two-fluid hollow cone nozzle with a spray angle of 70 °, and granulation and coating operations were performed.

2nd step

Bow I Continuing the rolling operation of the horizontal cylindrical mixer, spray coating the poorly water-soluble compounds shown in Tables 1-4 at 100 g / min using the same two-fluid hollow cone nozzle. Was done. Finally, fine powder was added as needed, and the rolling operation was continued for 60 seconds to obtain particles.

3rd step

Next, the fluidized bed (G 1 att—P atWREX, Model No. FD—WRT—20 manufactured by Parex Co., Ltd.) is filled, and after filling, a wind (air) at 15 ° C. is sent into the fluidized bed, and the particle size is reduced. A cooling operation was performed. The wind speed in the fluidized bed was adjusted in the range of 0.2 to 10. Om / s while checking the fluidized state. As a result, particles cooled to 20 ° C were obtained. The obtained particles are classified by using a sieve having a mesh size of 250 m and a mesh size of 2000 m, and pass through a sieve having a mesh size of 2000 m without passing through the mesh size of 250 m. The diameter, angle of repose, and bulk density are shown in Tables 1-4. Method for producing surface-treated water-soluble inorganic compound particles 4 (fluidized bed granulation)

1st step

Of the composition components shown in Tables 1 to 4 below, water-soluble inorganic compound core particles were placed in a fluidized bed (PAREX Co., Ltd., GI att—PWREX, model number FD—WRT—20), and the powder was left standing. A mass that gives a layer thickness of 200 mm was added. Then, a 50 ° C air (air) was sent into the fluidized bed, and after confirming that the powder had fluidized, the water-soluble polymer aqueous solution was sprayed from above onto the fluidized powder bed. The granulation and coating operations were performed while adjusting the wind speed in the fluidized bed in the range of 0.2 to 10. Om / s while checking the fluidized state. A two-fluid hollow cone nozzle with a spray angle of 70 ° was used for spraying the water-soluble polymer aqueous solution. The spray speed was about 100 gZmin. 2nd step

While maintaining the fluidized state in the fluidized bed, the coating operation was performed by spraying the poorly water-soluble compounds shown in Tables 1 to 4 at 100 gZmin using the same two-fluid hollow cone cone nozzle. .

At this time, when the water content exceeded 10% by mass, the powder was flowed while the wind (air) at 50 ° C was continuously fed into the fluidized bed until the water content became 8% by mass. Finally, when adding fine powder as required, the granulated material is discharged from the fluidized bed, and a rolling drum (0.6 m in diameter, 48 m in length, 1 mm in thickness, 12 cm in width, 12 cm in length and 48 cm in length) The granulated material and the fine powder were mixed for 60 seconds at a rotation speed of 2 Orpm with 4 plates.

3rd step

After the completion of the second step, the surface-treated water-soluble inorganic compound particles (average particle diameter, angle of repose, The bulk densities are shown in Tables 1-4). Production method of surface-treated water-soluble inorganic compound particles 5 (stirring granulation + tumbling granulation)

1st step

Of the compositions shown in Tables 1-4 below, water-soluble inorganic compound core particles were Into a Reedige mixer (M20 type, manufactured by Matsupo Corporation) with a clearance of 5 mm between the excavator and the wall (filling ratio: 30% by volume), and start stirring at 200 rpm at the main shaft. (The chopper was stopped.) 10 seconds after the start of stirring, an aqueous solution of a water-soluble polymer was added in 30 seconds, and granulation and coating operations were performed.

2nd step

The obtained granules are discharged from the Lodige mixer, and are fed into a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, container: 31.7 L, drum inner wall surface) (With two baffles with a clearance of 20 mm from the inner wall and a height of 45 mm)) and started rolling at a rotation speed of 22 rpm. Thirty seconds after the start of rolling, the poorly water-soluble compounds shown in Tables 1 to 4 were spray-added at 100 g Zmin using a two-fluid holo-cone nozzle with a spray angle of 70 °, and coating was performed. .

Finally, fine powder was added as needed, and the rolling operation was continued for 60 seconds to obtain surface-treated water-soluble inorganic compound particles.

3rd step

Then, the surface-treated water-soluble inorganic compound particles (average particle diameter, angle of repose, and bulk density are shown in Table 3) by the same operation as in the third step of the above-mentioned method 3 for producing the surface-treated water-soluble inorganic compound particles (rolling granulation). 1-4) were obtained.

In each of the methods 1 to 5 for producing the surface-treated water-soluble inorganic compound particles, the poorly water-soluble compound was added in a liquid state having a melting point or higher. In addition, coarse particles of surface-treated water-soluble inorganic compound particles which are not used as the surface-treated water-soluble inorganic compound particles generated in the classification process of the surface-treated water-soluble inorganic compound particles 1 to 5 are manufactured by Fimill (Hosokawa Micron Co., Ltd.) The mixture was ground using KA-3) (screen hole diameter: 1.2 mm, number of revolutions: 470 rpm), and put into a granulator together with a water-soluble inorganic compound at the next granulation and reused. Also, when fine particles of the sieved product not used as the surface-treated water-soluble inorganic compound particles were generated by the classification operation, the fine particles were also put into a granulator together with the water-soluble inorganic compound at the next granulation and reused.

In Comparative Examples a30, a31, and a33, a poorly water-soluble compound was not added, and in a32, a34, and a35, a water-soluble polymer compound was not added. In Comparative Example a29, neither the water-soluble polymer compound nor the poorly water-soluble compound was added, and Sodium carbonate (grain ash) was used as it was.

With respect to the obtained surface-treated water-soluble inorganic compound particles, the heat of dissolution of each surface-treated portion, the amount of heat generated by wetting of the surface-treated water-soluble inorganic compound particles, and the wetting rate of the surface-treated portion were measured and evaluated by the following methods. The results are shown in Tables 1-4.

(1) Measurement of heat of dissolution and dispersion of surface treatment

0.1 g of the obtained surface-treated water-soluble inorganic compound particles (sodium carbonate particles in Comparative Example a29) was measured and sealed in an ampoule tube having an inner diameter of lcm and a length of about 4 cm. Tubes were also enclosed to make blanks.

These were installed on a twin calorimeter (Multi-Micro Calorime Ichiichi MM C-51-111, manufactured by Tokyo Riko Co., Ltd.), and stored in a cell containing 25 mL of water. Thermal equilibration was performed under stirring conditions of 60 ° C. and 60 ° C. After confirming the stability of the baseline, break the ampoule tube with the hammer in the device and bring it into contact with water.Measure the change in the amount of heat associated with the dissolution and dispersion of the surface-treated water-soluble inorganic compound particles. The heat value (Q) during dissolution and dispersion of the compound particles was obtained.

Similarly, the calorific value (Q _A ) of the water-soluble inorganic compound core particles and the calorific value (Q _B ) of only the first surface treatment section were measured. The first surface treatment unit for heat generation in the solution or dispersion process in water, Q _B - means processing section that satisfies Q _A <0. The second surface treatment part that absorbs heat in the melting-decomposition process in water, refers to processing unit which satisfies the Q- Q _B> 0. In addition, the endothermic in the dissolution / dispersion process in the entire surface treatment section means a state of Q−Q _A > 0. Incidentally, Q, 0 and <3 ₃ were both exothermic (i.e., a negative value).

(2) Measurement of wet calorific value

10 g of the obtained surface-treated water-soluble inorganic compound particles (sodium carbonate particles in Comparative Test Example a29) were put into a glass filter with a 3 cm inside diameter and a 5 cm height plate, and then a Ripon-shaped temperature sensor was mounted. After placing, an additional 10 g of sample was placed. This was installed on the upper joint of the two-necked flask, and an aspirator was connected to the side joint. 10 g of water at 25 was placed on this, and the pressure was immediately reduced for 10 seconds to allow all the water to pass through and wet the surface of the surface-treated water-soluble inorganic compound particles. After that, the time change of the temperature detected by the temperature sensor 1 was measured, and the maximum temperature caused by the hydration reaction was determined. The amount of heat generated by wetting depends on the temperature before wetting (the surface treatment aqueous solution before wetting) Of the inorganic inorganic compound particles) and the maximum temperature after wetting, the maximum temperature rise was determined by the following equation.

Maximum temperature rise (° c) = (maximum temperature after wetting (° c)) -1 (temperature before wetting (° c)) Dissolution and dispersion of the obtained surface-treated water-soluble inorganic compound particles in the surface-treated part endotherm - and (Q Q _a), the relationship of the maximum degree of temperature increase due to the measurement of wet heating value, correlation was seen shows Suyo in Figure 1. This indicates that a large amount of heat absorbed by the dissolution reduces the amount of heat generated by wetting. Comparative Test Example a29 Although the maximum temperature rise of sodium carbonate particles in 29 is 31.6 ° C, the surface treatment aqueous solution whose heat of solution in the surface treatment part is in the range of 30 to 80 JZ g The temperature of the conductive inorganic compound particles is suppressed to a degree of temperature rise of 15 ° C to 6 ° C.

The obtained maximum temperature rise was evaluated based on the following evaluation criteria.

Evaluation criteria>

◎: Maximum temperature rise is 9 to 12 ° C

〇: Maximum temperature rise 6 to 9 ° C or 12 to 15 ° C

△: Maximum temperature rise is less than 6 ° C

X: Maximum temperature rise is 15 ° C or more

(3) Evaluation of the wetting rate on the surface of the surface-treated water-soluble inorganic compound particles (Noshnon method

0.5 g of surface-treated water-soluble inorganic compound particles (sodium carbonate particles in Comparative Example a29) sieved to 355 to 500 m, with a 1 cm inner diameter scale with a glass fill at the bottom Filled in a glass tube, immersed in water at 5 ° C up to a height of 0.6 cm from the bottom where the surface-treated water-soluble inorganic compound particles are filled, and then filled with the surface-treated water-soluble inorganic compound particles The time until water permeated to the top of the was measured. The obtained penetration time was evaluated based on the following evaluation criteria.

◎: Permeation time is 300 to 400 minutes

〇 to ◎: Permeation time is 200 to 300 minutes

〇: Permeation time is 100 to 200 minutes

X: Permeation time is less than 100 minutes or more than 400 minutes

(4) Evaluation of device adhesion After preparing the surface-treated water-soluble inorganic compound particles, the state of formation of deposits on the inner wall of the device where the particles were granulated was evaluated based on the following evaluation criteria.

Evaluation criteria>

A: Almost no deposits

〇: There is no problem with attached matter

△: noticeable deposits

X: Deposits are present on almost the entire surface.

Tables 1 to 4 show, in addition to the above evaluation results, the temperatures at which the used water-soluble inorganic compound core particles, water-soluble polymer compounds and poorly water-soluble compounds were used, and the temperatures after the second step in each production method. The temperature of the surface-treated water-soluble inorganic compound particles and the production method used for preparing each surface-treated water-soluble inorganic compound particle are also described.

[table 1]

[Table 2]

Real way

Composition [%]

all al2 al3 al4 al5 al6 al7 al8 al9 a20 Water-soluble sodium carbonate 82.0 82.0 84.0 84.0 84.0 87.0 81.0 82.0 83.0 80.0 Inorganic compound potassium carbonate

Sodium bicarbonate

Sodium sesquicarbonate

Water-soluble HPC--1.0 One--One---Polymer MA1 3.0 3.0-One--One---Compound MA2---3.0------

MA3 one-one-3.0 one-one--

PAS-one-one-3.0--one-

AG-one-one--0.5---

CMC--------1.0 One-

PAP--------3.0 Monosilicate

SRC 3.0 Poorly water-soluble Lauric acid 1 6.0 3.0 1 5.0 5.0 6.0 5.0-5.0 Compound Myristic acid 6.0

C. Lumitic acid--5.0-1-1--Stearic acid----1--5.0 1 C. Lumitic acid methyl ester

Asi'pic acid

Stearyl alcohol----------Fine powder Talc 3.0

ASi Ceolite-3.0 4.0 One--4.0 4.0 4.0 4.0 Moisture and other components Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Opening 100.0

Production method 1 3 4 4 4 5 4 4 2 5 Temperature of water-soluble inorganic compound core particle [° c] 55 44 45 60 44 46 44 44 70 45 Temperature of water-soluble polymer compound [° c] 45 51 45 50 50 50 50 50 65 50 Temperature of poorly water-soluble compound [° c ^] 60 51 50 63 60 61 58 57 70 60 Surface treatment after 2nd step

Temperature of water-soluble inorganic compound particles [° C] 60 50 52 65 54 56 55 54 80 54 Maximum temperature rise of heat generation value of moistening ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Permeation time of Bash bang method [min] ◎ ◎ 〇 ◎ ◎ ◎ 〇 ◎ ◎ ◎ Equipment adhesion ◎ ◎ 〇 ◎ OO ◎ ◎ 〇平均 Average particle diameter of particles [μπι] 340 340 400 400 380 385 550 500 420 580 Particle repose angle [°] 40 40 45 35 30 30 45 45 45 45 Bulk density of particles [ein ³ ] 1.07 1.07 1.03 1.05 1.08 1.07 0.92 0.94 1.00 0.90

[Table 3]

[Table 4]

[Preparation examples b1 to b7]

Surfactant-containing particles b1 to b7 were obtained by the following production method.

Preparation method of surfactant-containing particles 1

According to the composition shown in Table 5 below, surfactant-containing particles b1 were prepared in the following procedure. First, water was poured into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, a surfactant excluding α-SF-Na and a nonionic surfactant, and PEG # 6000 were added and stirred for 10 minutes. Then MA1 (acrylic acid (Maleic acid copolymer sodium salt) and a fluorescent agent. After stirring for an additional 10 minutes, a portion of powdered zeolite A (2.0% equivalent (to each particle, the same applies hereinafter)) is added during kneading, 3.2% equivalent of a milling aid, .5% of each type A zeolite for surface coating), sodium carbonate, carbonated lime and sodium sulfite. After stirring for another 20 minutes to prepare a slurry for spray drying with a water content of 38%, the slurry was spray-dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C to obtain an average particle diameter of 320 ^ m and a bulk density of 0 Spray-dried particles with 30 g Z cm ³ and 5% moisture were obtained, while the fatty acid ester of the raw material was sulfonated and neutralized to obtain an aqueous slurry of α-SF-Na (water concentration 25%). Then, a part of nonionic surfactant (Q! —SF—25% based on Na) is added, and the water content is reduced under reduced pressure with a thin film dryer to 11%, and one SF—Na and nonion are added. A mixed concentrate of surfactant was obtained.

The spray-dried particles described above, this mixed concentrate, 2.0% equivalent of zeolite A, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition are continuously added in a continuous manner. (KRC-S4 type, manufactured by Kurimoto Tetsusho Co., Ltd.) and kneaded under conditions of a kneading capacity of 120 kgZhr and a temperature of 60 ° C to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded material is extruded using a Pellet Yuichi Double (manufactured by Fuji Padal Co., Ltd., EXDF JS-100 type) equipped with a die with a hole diameter of 10 mm, and cut with a cutter (the peripheral speed of the cutter is 5 ms) A pellet-like surfactant-containing molded product having a length of about 5 to 30 mm was obtained.

Next, 3.2% equivalent of particulate A-type zeolite (average particle size: 180 m) as a grinding aid was added to the obtained pellet-like surfactant-containing molded product, and cooled air (10 ° C, 15 mZs) was added. ) Pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in three stages in coexistence (screen hole diameter: 1st stage Z2 stage 3rd stage = 12mm / 6mmZ3mm, rotation speed: 1st stage / 2nd stage All 3rd stages are 4700 rpm). Finally, a horizontal cylindrical tumbling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, container: 131.7 L drum inner wall with 20 mm clearance from the inner wall and two baffles 45 mm high) Under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C, 1.5% equivalent of fine powder type A zeolite was added. While spraying 0.5% equivalent of nonionic surfactant and perfume, it was tumbled for 1 minute to modify the surface to obtain particles.

In order to color some of the obtained particles, the surfactant-containing particles were transported on a belt conveyor at a speed of 0.5 mZ s (the height of the surfactant-containing particle layer on the belt conveyor was 30 mm, and the A 20% aqueous dispersion of the dye was sprayed on the surface to obtain surfactant-containing particles bl (average particle diameter 550 zm, bulk density 0.84 g / cm ³ ).

Surfactant-containing particles b2 and b3 (average particle diameter and bulk density are described in Table 5) were obtained in the same manner as the method for preparing surfactant-containing particles b1. Preparation method of surfactant-containing particles 2

According to the composition shown in Table 5 below, surfactant-containing particles b4 were prepared in the following procedure. Of the components shown in Table 5 below, all components (temperature 25 ° C) except for surfactants and 5.0% equivalent of P-type zeolite, pigments, and fragrances used for surface coating were subjected to a plow blade excavator. Equipped with an excavator and a clearance meter between the excavator and the wall with a clearance of 5 mm (a filling ratio of 50% by volume, manufactured by Matsupo Co., Ltd., M20), and agitated the main spindle at 200 rpm and the chopper at 200 rpm. . 30 seconds after the start of stirring, a surfactant mixture (a mixture of a nonionic surfactant and an anionic surfactant preliminarily heated to 60 ° C and uniformly mixed) and water (temperature 60 ° C) were added in 2 minutes, Agitation granulation was continued at a jacket temperature of 30 ° C. until the average particle diameter reached 400. Finally, 5.0% equivalent of P-type zeolite was added and stirred for 30 seconds to modify the surface to obtain particles.

In order to color some of the obtained particles, a 20% aqueous dispersion of the pigment is sprayed in the same manner as in the method 1 for preparing the surfactant-containing particles, and the surfactant-containing particles b 4 (average particle diameter 400 m and a bulk density of 0.80 gZcm ³ ) were obtained. Preparation method of surfactant-containing particles 3

According to the composition shown in Table 5 below, surfactant-containing particles b5 were prepared by the following procedure. Among the compositions shown in Table 5 below, nonionic surfactants, powdered zeolite A (zeolite) For kneading a part of Olite A) (2.0% equivalent (each particle, same hereafter)) during kneading, 3.2% equivalent for milling aid, 1.5% equivalent for surface coating After excluding the A-type zeolite of the above), components other than pigments and perfumes are dissolved or dispersed in water to prepare a slurry with a water content of 38%, and then sprayed using a countercurrent spray-drying tower at a hot air temperature of 300. It was dried to obtain spray-dried particles having an average particle diameter of 330 wm, a bulk density of 0.30 gZcm ³ and a water content of 3%. Along with the dried particles, 2.0% equivalent of zeolite A, 0.5% equivalent of nonionic surfactant and water other than for spray addition were continuously added to the powder by Kurimoto Tetsusho Co., Ltd. (KRC-S4 type) and kneaded under the conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C to obtain a surfactant-containing kneaded product.

The surfactant-containing kneaded material was extruded using a pellet doubler (EXDF JS-100, manufactured by Fuji Padal Co., Ltd.) equipped with a die with a hole diameter of 10 mm, and was cut with a cutter (one round of cutlery). A pellet-like surfactant-containing molded product having a speed of 5 m / s) and a length of about 5 to 30 mm was obtained.

Next, the obtained pellet-like surfactant-containing molded product was pulverized by the same method as in the method 1 for preparing surfactant-containing particles, and then subjected to surface modification to obtain particles. In order to color some of the obtained particles, a 20% aqueous dispersion of the pigment is sprayed in the same manner as in the method 1 for preparing the surfactant-containing particles, and the surfactant-containing particles b 5 (average particle diameter 540 m and a bulk density of 77 gZcm ³ ).

Surfactant-containing particles b7 (average particle diameter and bulk density are described in Table 5) were obtained in the same manner as the method for preparing surfactant-containing particles b5. Preparation method of surfactant-containing particles 4

According to the composition shown in Table 5 below, surfactant-containing particles b6 were prepared in the following procedure. First, water was charged into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. Sodium sulfate and a fluorescent agent were added thereto, and the mixture was stirred for 10 minutes. Subsequently, after sodium carbonate was added, PAS (sodium polyacrylate) was added, and the mixture was further stirred for 10 minutes, and then sodium salt and a part of powdered A-type zeolite were added. Further, the mixture was stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the obtained slurry for spray drying was 50 ° C. This slurry is pressure Spray drying is carried out with a counter-current spray dryer equipped with a nozzle, with a water content of 3% and a bulk density of 0

Spray-dried particles having a particle size of 50 gZcm ³ and an average particle size of 250 m were obtained.

Separately, a nonionic surfactant, PEG # 6000, and anionic surfactant were mixed at a temperature of 80 ° C. to prepare a surfactant composition having a water content of 10%. LAS—Na was used in the form of a solution neutralized with an aqueous sodium hydroxide solution.

The obtained spray-dried particles are charged (filling rate 50% by volume) into a Reedige mixer (M20 type, manufactured by Matsupo Co., Ltd.) equipped with a plow blade-shaped shovel and having a clearance between the shovel and the wall of 5 mm, and a jacket Then, stirring of the spindle (150 rpm) and the chopper (4000 rpm) was started while flowing hot water at 80 ° C at a flow rate of 10 LZ. The surfactant composition prepared above was added thereto over 2 minutes, and then stirred for 5 minutes. Then, the layered silicate (SKS_6, average particle size 5 / m) and a part of powder A zeolite were used. (Equivalent to 10%) and stirred for 2 minutes to obtain particles.

The obtained particles and a part of powder A-type zeolite (equivalent to 2%) are mixed with a V blender, and after spraying a fragrance, a surfactant is used to color some of the surfactant-containing particles. It was sprayed with a 20% aqueous dispersion of the dye in the same manner as in preparation method 1 containing particles, give the interfacial active agent-containing particles b 6 (average particle size 300 / m, the bulk density 0. 75 g / cm ³⁾ Was.

Five]

[Example of preparation of granulated bleach activator]

Preparation method of bleach activator granule A

70 parts by weight of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals, Inc.), 20 parts by weight of PEG # 6000, and 5 parts by weight of AOS-Na powder as bleach activator The product was supplied to Extrude® OMICS EM-6 manufactured by Hosokawa Micron Corp., kneaded and extruded (kneading temperature 60 ° C) to obtain a noodle extruded product with a diameter of 0.8 mm <i). The extruded product (cooled to 20 ° C by cold air) is introduced into Fitzmill DKA-3 manufactured by Hoso Kamicron Co., Ltd. In addition, 5 parts by mass of A-type zeolite powder is supplied as an auxiliary in the same manner, and ground. A bleach activator granule A having an average particle diameter of about 700 am was obtained. Preparation method of bleach activator granulated product B A bleach activator granule B was prepared in the same manner as the bleach activator granule A, except that sodium 4-dodecanoyloxybenzenesulfonate was used as the bleach activator. Preparation method of granulated bleach activator C

A bleach activator granule C was prepared in the same manner as the bleach activator granule A, except that sodium 4-nonanoyloxybenzenesulfonate was used as the bleach activator.

[Examples 1-35, Comparative Examples 1-4]

According to the compositions shown in Tables 6 to 10 below, a granular detergent composition was prepared by the following method, and the solubility (low-temperature aggregation rate), the solidification property (solidification rate), and the fluidity were evaluated. The results are shown in Tables 6 to 10. Preparation of granular detergent composition

Horizontal cylindrical tumbling mixer (cylinder diameter 585 mm, cylinder length 490 mm, vessel 1 31.7 L drum inner wall clearance 20 mm, height 45 mm (With two baffles) at a filling rate of 30% by volume, a rotation speed of 22 rpm, and a temperature of 25 ° C. (a) surface-treated water-soluble inorganic compound particles described in Tables 1 to 4; The surfactant-containing particles (b) described in 5 and other components were mixed for 5 minutes according to the compositions shown in Tables 6 to 10 to obtain a granular detergent composition. Tables 6 to 10 show the average particle size and bulk density of the obtained granular detergent composition.

(1) Evaluation of solubility (low-temperature aggregation rate)

5 g of the granular detergent composition was gently poured into a Petri dish containing 80 mL of 5 water and allowed to stand for 5 minutes. After standing, water is passed through a sieve with openings of 3360 together with the petri dishes, and the detergent composition remaining on the sieve is dried at 60 ° C for 2 hours. The mass after drying was measured, and the low-temperature agglomeration rate% was determined using the following equation.

Dry mass of detergent composition left on sieve

Low-temperature aggregation rate (%) = X100

Amount of granular detergent composition put in sieve The relationship between the low-temperature aggregation rate and the usability determined above is shown below. Considering the usability at home, the detergent composition preferably has a low-temperature aggregation rate of less than 20%.

Good: Low-temperature aggregation rate is less than 5%

Normal: Low-temperature aggregation rate of less than 520%

Poor: Low-temperature aggregation rate is less than 20 40%

Very bad: Low-temperature coagulation rate of 40% or more

(2) Evaluation of solidification (solidification rate)

Paper container consisting of three layers of coated pole paper (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) from the outside Using (moisture permeability 25 gZm ² * 24 hours (40 ° C 90 RH)), a box having a length of 15 cm, a width of 9.3 cm and a height of 18.5 cm was prepared. Put 1.2 kg of the granular detergent composition in this box, store in a recycle constant temperature and humidity room at 25 ° C (65% RH for 8 hours) and 45 ° C (85% RH for 16 hours) for 30 days, A sample for solidification test was obtained. After storage over time, the detergent was gently transferred to a sieve having an opening of 4 mm, solidified on the sieve, the remaining detergent was weighed, and the solidification rate was determined by the following formula. Mass of detergent composition left on sieve

(Y < ₌ X 丄 00

The relationship between the solidification rate and the usability determined above is shown below. Considering the usability at home, the detergent composition preferably has a solidification rate of less than 20%.

Good: Solidification rate is less than 5%

Normal: Solidification rate less than 5-20%

Bad: solidification rate less than 20 40%

Very bad: solidification rate of 40% or more

(3) Evaluation of liquidity

The angle of repose was measured by the below-described method of measuring the angle of repose using the granular detergent composition after the evaluation of the solidification property. The results were evaluated according to the following evaluation criteria. Considering the usability at home, the detergent composition preferably has a repose angle of 60 ° or less. Evaluation criteria>

〇: Angle of repose is 50 ° or less

Δ: Angle of repose is 50. Over 60 ° or less.

X: Angle of repose exceeds 60 °

The average particle diameter, bulk density and angle of repose in the present invention were measured by the following methods.

(4) Measurement of average particle size

For each sample and its mixture, use a 9-stage sieve and pan of 1680 fim, 1410 xm, 1 190 urn, 1000 m, 710 / m, 500 ^ m, 350 τη, 250 ^ m, 149 rn, To perform a classification operation. Classification is performed by stacking small sieves with large sieves in a tray in the order of the sieves, putting 100 g / base sample from the top of the top 168 m sieve, and closing the lid. After being attached to a low-tap type sieve shaker (Iida Seisakusho Co., Ltd., tapping: 156 times, rolling: 290 times / minute), and vibrated for 10 minutes, the sample remaining on each sieve and tray was removed. The sample was collected for each sieve and the mass of the sample was measured.

When the mass frequency of the saucer and each sieve is integrated, the opening of the first sieve at which the integrated mass frequency is 50% or more is defined as am, and the opening of the sieve one step larger than am is defined as bm. The average particle diameter (weight 50%) was determined by the following formula, where the integration of the mass frequency from the sieve to the am sieve was c%, and the mass frequency on the am sieve was d%.

(50- (c-d / (logb-loga) X 1 ogb)) / (d / (logb-loga)) Average particle size (weight 50%) = 10

(5) Measurement of bulk density

The bulk density was measured according to JIS K3362-1998.

(6) Measurement of angle of repose

The angle of repose was measured using a turntable type angle of repose meter manufactured by Tsutsui Physical and Chemical Instruments Co., Ltd. [Table 6]

[Table 7]

Example

Composition [%]

8 9 10 11 12 13 14 a Particle type a9 a9 a9 a9 a9 a6 a6 Blending amount 10.0 15.0 20.0 30.0 40.0 10.0 20.0 b Particle bl [%] One-one----b2 [%] 83.8 78.8 73.8 63.8 53.8 83.8 73.8 b3 [%]---one one-one

M [%]---1-1-b5 [%]---1--b6 [%] 1-1-1-b7 [%]--1-1-1-Enzyme particles A 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme particles B 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Sodium percarbonate 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Bleaching activator Type AAAAACC Granulated compounding amount 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Total L% '' 100.0

Average particle size [/ m] 538 527 516 494 472 538 516 Bulk density `` g / cm ³ l 0.87 0.88 0.90 0.93 0.96 0.87 0.90 Low-temperature aggregation rate [%] 0 0 0 0 0 0 0 Solidification rate [%] 0 0 0 0 5 0 0 Liquidity 〇〇〇〇〇〇〇 [Table 8]

[Table 9]

[Table 10]

[Examples 36 to 52]

Spraying at the time of preparing surfactant-containing particles in Examples 1 to 17, either or both of a fragrance and a nonionic surfactant, surface-treated water-soluble inorganic compound particles, surfactant-containing particles and other particles The components were sprayed when powder was mixed in a horizontal cylindrical tumbling mixer to obtain a granular detergent composition (Examples 36 to 52). Also in this granular detergent composition, the same evaluation results as in Examples 1 to 17 were obtained.

[Example 53 to 69]

In Examples 1 to 17, the dye aqueous dispersion sprayed at the time of preparing the surfactant-containing particles was subjected to surface-treated water-soluble inorganic compound particles, surfactant-containing particles, and other particle components in a horizontal cylindrical tumbling mixer. After powder mixing, the mixture was sprayed by the same method as described in Method 1 for preparing surfactant-containing particles to obtain a granular detergent composition (Examples 53 to 69). Also in this granular detergent composition, the same evaluation results as in Examples 1 to 17 were obtained.

[Examples 70 to 83]

In Example 4, the surface-treated water-soluble inorganic compound particles a 9 Except having changed to 3, a12, and a16 particles, it prepared similarly to Example 4 and obtained the granular detergent composition (Examples 70-74). With this granular detergent composition, the same evaluation results as in Example 4 were obtained.

Further, in Example 30, except that the a18 particles, which are the surface-treated water-soluble inorganic compound particles, were changed to all, a13 to a15, and a20 to a24 particles. Preparation was performed in the same manner as in Example 30 to obtain a granular detergent composition (Examples 75 to 83). The same evaluation results as in Example 30 were obtained with this granular detergent composition.

40 g of the granular detergent composition of Example 4 and 40 g of the granular detergent composition of Comparative Example 2 were divided into six parts each of a pulse of a fully automatic washing machine “MAW-V8TP” manufactured by Mitsubishi Electric Corporation. It was placed in a conical cluster near the outer periphery of one of the fan-shaped depressions. 3 kg of clothing (50% of cotton underwear, 50% by weight of polyester Z cotton blended shirt) was put into a washing tub so as not to disturb the state of aggregation of the detergent composition. 38 L of tap water at 10 ° C was injected at a flow rate of 10 LZ so that water did not directly hit the detergent. We washed in the "wash quickly" course, a short-time washing course. After completion of the washing process (3 minutes), drainage was performed, and the state of the detergent composition remaining in clothing and the washing tub was visually determined. In Comparative Example 2, a large amount of aggregates of the detergent composition remained, whereas in Example 4, no detergent composition remained. The granular detergent composition of Example 4 and the granular detergent composition 4 of Comparative Example 3 did not. 0 g of the pulsator of the fully automatic washing machine “ASW-ZR750” manufactured by Sanyo Electric Co., Ltd. placed. 3 kg of clothing (50% by mass of cotton underwear, 50% by mass of polyester cotton blend) was put into a washing tub so as not to destroy the detergent composition. 39 L of 10 ° C tap water is injected at a flow rate of 10 L / min so that water does not directly hit the detergent composition. Washed. After the washing process (8 minutes), the drainage was carried out, and the state of the clothes and the detergent remaining in the washing tub was visually judged. In Comparative Example 3, a large amount of aggregates of the detergent composition remained, whereas in Example 4, no detergent composition remained.

About the granular detergent composition of Example 4 and the granular detergent composition of Comparative Example 3, using a drum type washing machine with a detergent inlet (manufactured by Sharp Corp., ES-E61), the inlet was used. 40 g of the granular detergent composition was added and washed on a standard course (water temperature 10 ° C, water volume 30 L, clothing 3 kg (cotton underwear 50% by mass, polyester / cotton blended shirt 50% by mass)). When this washing was repeated once a day for 30 days, the detergent composition remained undissolved at the inlet in Comparative Example 3 (about 10 g), whereas the detergent composition did not remain in Example 4 .

The raw materials used in the examples are shown below.

(Water-soluble inorganic compound core particles)

• Sodium carbonate: Tsubuhai (Asahi Glass Co., Ltd., average particle size 320 m, bulk density 1. 07 g Roh cm ³⁾

· Sodium sesquicarbonate: Ses QUi TM Sodium Ses qu icarbonate (FMC, USA, average particle size 290 zm, bulk density 0.75 g / cm ³ )

• Carbonated rim: Carbonated rim (powder) (manufactured by Asahi Glass Co., Ltd., average particle diameter 490 m, bulk density 1.30 g / cm ³ )

· Sodium bicarbonate: sodium bicarbonate (made by Asahi Glass Co., Ltd.)

• Sodium sulfate: neutral anhydrous sodium sulfate (Nippon Chemical Industry Co., Ltd.)

• Sodium sulfite: Anhydrous sodium sulfite (Shinshu Chemical Co., Ltd.)

• Sodium chloride: Nissei no Yaki salt C (manufactured by Nippon Salt Co., Ltd.)

• Layered silicate: crystalline layered sodium gateate, SKS-6 (manufactured by Clariant Japan Co., Ltd.)

(Water-soluble polymer compound)

• HPC: Hydroxypropylcellulose (HPC, S SLT yp e, manufactured by Nippon Soda Co., Ltd.) Diluted with water to a pure content of 5%

• MA1: Acrylic / maleic acid copolymer Na salt, Aquaric TL-400 (Nippon Shokubai Co., Ltd.) (40% pure water solution)

• MA2: acrylic acid-nomaleic acid copolymer Na salt: Aqualic TL-1400 (manufactured by Nippon Shokubai Co., Ltd.) diluted with water to a pure content of 20%

• MA3: Acrylic acid / maleic acid copolymer Na salt: Sokal an CP45 (manufactured by BASF) diluted with water to a pure content of 20% • PAS: Polyacrylic acid Na salt, Aquaric DL-40 (Nippon Shokubai Co., Ltd.) 40% pure solution

• AG: 4% pure aqueous solution of sodium alginate and duck algin NSPLL (manufactured by Kibun Food Chemifa Corporation)

· CMC: Ripoxymethylcellulose Na, 5% pure solution of CMC Daicel 1105 (manufactured by Daicel Chemical Industries, Ltd.)

• PVA: Polyvinyl alcohol, Kuraray Poval PVA-105 (Kuraray Co., Ltd.) 5% pure solution

• PAP: Polyaspartic acid sodium, Baypure DS 100/40% (manufactured by Bayer, pure 40% aqueous solution)

• Silates: Nippon Kagaku Kogyo No. 1 sodium silicate (45% aqueous solution)

• PEG # 6000: polyethylene glycol manufactured by Lion Corporation, trade name PEG

• 6000M

• S RC: Clariant Japan Co., Ltd. Soil Release Polymer, Texc a re SRN— 325, 25% aqueous solution

(Poorly water-soluble compound)

• Lauric acid: manufactured by NOF Corporation, NAA-122, melting point 43 ° C

• Myristic acid: Myristic acid, manufactured by Shin Nippon Rika Co., Ltd., melting point 52 ° C

• Palmitic acid: Nippon Rika Co., Ltd., palmitic acid P, melting point 58 ° C

'Stearic acid: Nippon Rika Co., Ltd., Snow Brand Stearic acid 5000, melting point 65 ° C' Palmitic acid methyl ester: Lion Co., Ltd., Pastel M-16, melting point 30 ° C

-Adipic acid: Sumitomo Chemical Co., Ltd., melting point 151 ° C

• Stearyl alcohol: manufactured by Shin Nippon Rika Co., Ltd., Conol 3 O S S, melting point 57 ° C (fine powder)

• A-type zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure)

• P-type zeolite: D〇UC I L A24 (Ineso Silica)

• Talc: Micro Ace LG (Nippon Talc Co., Ltd.)

(Surfactant) -α-SF-Na: 14 carbon atoms: 16 = 18: 82 sodium salt of methyl sulfo fatty acid methyl ester (manufactured by Lion Corporation, AI = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate) , Methyl sulfate, hydrogen peroxide, water, etc.)

• LAS-K: Linear alkyl (10-14 carbon atoms) benzenesulfonic acid (Lipo> LH-200 (Lion Co., Ltd.) LAS-H pure content 96%) was added to 48% water at the time of preparing the surfactant composition. Neutralize with potassium oxide solution). The blending amounts in Table 5 indicate mass% as LASK.

• LAS-Na: linear alkyl (10-14 carbon atoms) Benzenesulfonic acid (Lybon LH-200 (LAS-H pure content 96%) manufactured by Lion Co., Ltd.) was added to 48% water at the time of preparing the surfactant composition. Neutralize with aqueous sodium oxide). The blending amounts in Table 5 indicate mass% as LAS-Na.

• AOS—K: having an alkyl group with 14 to 18 carbon atoms—potassium olefin sulfonate (manufactured by Lion Corporation)

• AOS—Na: powdered sodium alpha-leufine sulfonate having 14 carbon atoms (trade name: Lipolan P J-400, manufactured by Lion Corporation)

• stone鹼: carbon atoms 12: fatty acids L 8 Natoriumu (Lion Co., Ltd., purity: 67%, titer: 40 to 45 ° C, fatty acid _{composition: C 12:. L l 7} %, C 14: _{0. 4%, C 16: 29.} 2%, C 18 F 0 ( _{stearic): 0. 7%, C 18} F 1 ( O maleic _{acid): 56. 8%, C 18} F 2 ( linoleic acid) : 1.2%, molecular weight: 28 9)

• AS—Na: Sodium alkyl sulfate having an alkyl group with 10 to 18 carbon atoms (Sandet LNM manufactured by Sanyo Chemical Industries, Ltd.)

• Nonionic surfactant A: Oxidized styrene averaged 8 mol adduct of Diadol 13 (manufactured by Mitsubishi Chemical Corporation) (90% pure content)

• Nonionic surfactant B: ECOROL 26 (alcohol with alkyl group having 12 to 16 carbon atoms, manufactured by E COGRE EN), average 15 mol ethylene oxide adduct (90% pure)

(Dye) • Dye A: Ultramarine (Dainichi Seika Kogyo Co., Ltd., U1 tramarine Blue)

• Dye B: Pigment Green 7 (Dainichi Seika Kogyo Co., Ltd.)

• Dye C: Acrylonitrile / styrene / acrylic acid as the constituent monomer. Spherical resin particles with an average particle diameter of 0.35 xm obtained by radical emulsion polymerization in a water dispersion system. I. BAS IC RED-1 is an aqueous dispersion of a pink fluorescent pigment obtained by adding the polymerized resin suspension to a suspension and subjecting it to heat treatment.

(Fragrance)

• Perfume A: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]

· Fragrance B: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18]

• Fragrance C: Fragrance composition C shown in JP-A-2002-146399 [Table 11] to [Table 18]

• Perfume D: Perfume composition D shown in JP-A-2002-146399 [Table 11] to [Table 18]

(Enzyme)

• Enzyme particles A: Kannaze 12 T (Nopozymes) ZL I PEX50T (Nopozymes) Z Termamil 60T (Nopozymes) / Selzym 0.7T (Nopozymes) = 5Z2Zl / 2 (mass ratio)

· Enzyme particles B: Evarase 8T (Nopozims) ZL I PEX50T (Nopozims) Evenmamil 60T (Nopozims) / Selzym 0.7T (Nopozims) = 5Z2Zl / 2 (mass ratio)

(Other)

• Fluorescent agent: Tinopearl CBS—X (Ciba Specialty Chemicals) / Tinopar AMS—GX (Ciba Specialty Chemicals) = 3Z1 (mass ratio) mixture • Sodium percarbonate: Mitsubishi Gas Chemical, SPC—D, Effective Oxygen content 13.2%, average particle size 760 m

Claims

The scope of the claims

1. The water-soluble inorganic compound core particles are subjected to a surface treatment with an organic or inorganic water-soluble polymer compound as a first surface treatment agent, and the treated surface is treated with a second water-insoluble compound as a second surface treatment agent. Surface-treated water-soluble inorganic compound particles.

2. A water-soluble inorganic compound core particle, a first surface treatment portion containing a water-soluble polymer compound formed on a part or the whole surface of the particle surface, and a part or the whole surface of the first surface treatment portion surface 2. The surface-treated water-soluble inorganic compound particles according to claim 1, further comprising a second surface-treated portion containing a poorly water-soluble compound formed on the surface.

3. The first surface treatment section exhibits exothermicity in the process of dissolving or dispersing in water, the second surface treatment section exhibits endothermicity in the process of dissolving or dispersing in water, 3. The surface-treated water-soluble inorganic compound particles according to claim 2, wherein all the surface-treated portions comprising the surface-treated portion exhibit endothermic properties in a process of dissolving or dispersing in water.

4. The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 3, wherein the water-soluble inorganic compound core particles are sodium carbonate or potassium carbonate.

5. The water-soluble polymer compound is one or more selected from a vinyl polymer compound, a polysaccharide, a derivative thereof, and a polyester polymer compound. 2. The surface-treated water-soluble inorganic compound particles according to claim 1.

6. The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 4, wherein the water-soluble polymer compound is a compound having a hydroxyl group.

7. The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 4, wherein the water-soluble polymer compound is water glass.

8. The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 7, wherein the poorly water-soluble compound is an anionic surfactant acid precursor and / or a salt thereof.

9. The anionic surfactant acid precursor is a fatty acid,

Item 8. The surface-treated water-soluble inorganic compound particles according to item 8.

10. The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 9, which is an alkaline agent for blending a granular detergent composition.

11. A method for producing surface-treated water-soluble inorganic compound particles including the following first step and second step.

12. The production method according to claim 11, wherein the poorly water-soluble compound is an anionic surfactant acid precursor.

13. The production method according to claim 12, wherein the temperature of the surface-treated water-soluble inorganic compound particles immediately after the completion of the second step is equal to or higher than the melting point of the anionic surfactant acid precursor.

14. (a) The surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 10, and (b) surfactant-containing particles containing a surfactant and an inorganic compound. A granular detergent composition comprising:

15. The granular detergent composition according to claim 14, wherein (b) the surfactant-containing particles contain a water-soluble polymer compound.

16. (a) The compounding amount of the poorly water-soluble compound in the surface-treated water-soluble inorganic compound particles is less than 10% by mass, and (b) the compounding amount of the surfactant in the surfactant-containing particles is 10 to 50% by mass. 16. The granular detergent composition according to claim 14, wherein the composition is:

17. A washing bath containing the surface-treated water-soluble inorganic compound particles according to any one of claims 1 to 10 and a laundry are performed at a bath ratio of 7 to 15 LZ kg and a washing temperature of 5 to 12 ° C. Washing method.