JP5356681B2 - Detergent composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition having high dissolvability and dispersiveness at low water temperature and high detergency for clothes. <P>SOLUTION: The detergent composition contains endothermic particles (A) including a water-soluble endothermic substance (a) and exothermic particles (B) including a water-soluble exothermic substance (b), and a mass ratio [(A)/(B)] of the endothermic particles (A) to the exothermic particles (B) is 0.05-4. As for the water-soluble endothermic substance (a), sodium chloride, sodium thiosulfate pentahydrate, and ammonium sulfate are preferable, while for the water-soluble exothermic substance (b), sodium carbonate and sodium thiosulfate are preferable. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a detergent composition having good solubility particularly at a low water temperature and a method for producing the same.

  Powdered or granular detergents are strongly aimed at increasing bulk density and reducing the amount of use for the convenience of consumers. These granular detergents having a high bulk density are desirably dissolved and dispersed quickly in water. However, in recent years, washing machines have been reduced in water consumption, low temperatures, and shortened operation time due to a decrease in bath ratio due to an increase in size, environmental and energy issues, and economic efficiency. It is a factor that lowers the dispersion and solubility of powdered or granular detergents. For this reason, there exists a problem that the undissolved residue of these powdery and granular detergents may remain on clothes especially at the time of washing in winter when the water temperature is low.

  On the other hand, depending on the state of use, a powdery or granular detergent may be put in one place in a washing machine with a supply device. In such a case, only the surface of the detergent in contact with the low-temperature washing liquid may be partially dissolved to generate a high concentration region of the inorganic salt contained in the detergent. When that happens, the high concentration region of the inorganic salt is rapidly cooled in the surrounding low temperature region, the crystals are precipitated, and the particles are firmly bonded to each other, so that the aggregate of detergent particles cannot be dispersed and becomes a paste, There may be a case where a phenomenon that remains in clothing occurs. This phenomenon is more likely to occur when the temperature of the washing liquid is 10 ° C. or lower, particularly 5 ° C. or lower.

  As an attempt to improve dispersibility and solubility in order to solve such a problem at a low water temperature, for example, it is known to make the particle size distribution of a cleaning agent a specific distribution (see, for example, Patent Document 1). ). It is also known to control the dissolution rate of the entire particle by specifying the composition of the cleaning agent (see, for example, Patent Document 2). It is also known to add alkaline filler particles to granular detergent dough (see, for example, Patent Documents 3 and 4).

However, the technique of Patent Document 1 requires a great deal of effort to adjust the particle size distribution, and remarkably narrows the compositional freedom of the cleaning agent. Moreover, in the detergent which mix | blended the water-soluble exothermic inorganic compound highly, the method described in these literatures is not enough in the effect of preventing undissolved residue.
Japanese Patent Laid-Open No. 11-35998 Japanese Patent Laid-Open No. 08-218093 Japanese Patent Laid-Open No. 62-167399 JP-A-62-253699

  An object of the present invention is to provide a detergent composition having good solubility and dispersibility at a low water temperature and having high detergency for clothes and a method for producing the same.

The present invention provides the following inventions.
1. A detergent composition comprising an endothermic particle (A) containing a water-soluble endothermic substance (a), an exothermic particle (B) containing a water-soluble exothermic substance (b), and a surfactant,
The detergent composition contained so that mass ratio [(A) / (B)] of the said endothermic particle (A) and the said exothermic particle (B) may be 0.05-4.
2. The water-soluble endothermic substance (a) is selected from sodium chloride, sodium thiosulfate pentahydrate, and ammonium sulfate, and the water-soluble exothermic substance (b) is selected from sodium carbonate and sodium thiosulfate. The detergent composition according to claim 1.
3. The detergent composition according to claim 1 or 2, wherein the endothermic particles (A) have an average particle size of 1 to 1200 µm and the exothermic particles (B) have an average particle size of 1 to 1200 µm.
4). The detergent composition according to any one of claims 1 to 3, wherein the exothermic particles (B) contain the water-soluble exothermic substance (b) and at least a surfactant.
5. It is a manufacturing method of the detergent composition according to any one of claims 1 to 4,
A step of obtaining a slurry comprising the water-soluble exothermic substance (b) and other components blended as necessary;
Spray drying the slurry to obtain base particles;
A step of loading the base particles with a surfactant to obtain exothermic particles (B);
Mixing the endothermic particles (A) and the exothermic particles (B);
The manufacturing method which has.
6). The production method according to claim 5, wherein the other components include a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt.

  The detergent composition of the present invention has good solubility and dispersibility at a low water temperature of 5 ° C. or less, and has a high detergency for clothes.

<Detergent composition>
The detergent composition of the present invention comprises an endothermic particle (A) containing a water-soluble endothermic substance (a), an exothermic particle (B) containing a water-soluble exothermic substance (b), a surfactant, and other if necessary. These components can be obtained by mixing.

  In the cleaning composition of the present invention, the surfactant and other components are made into a particle form together with one or both of the endothermic particles (A) and the exothermic particles (B), and then the endothermic particles (A) and the exothermic particles. What mixed the active particle (B) may be used.

  In the following, an endothermic particle (A) containing a water-soluble endothermic substance (a), an exothermic particle (B) containing a water-soluble exothermic substance (b) and a surfactant, and other components as necessary. Including embodiments will be described.

[Endothermic particles (A) containing a water-soluble endothermic substance (a)]
The endothermic particles (A) contain a water-soluble endothermic substance (a) and other components as required.

  The water-soluble endothermic substance (a) has a heat of dissolution in water of 1 to 120 kJ / mol, preferably 1 to 80 kJ / mol, more preferably 3 to 50 kJ / mol.

  Examples of the water-soluble endothermic substance (a) include inorganic salts, saccharides, amino acids, urea and the like. Specific examples include sodium chloride, sodium thiosulfate pentahydrate, ammonium sulfate, potassium sulfate, ammonium hydrogen carbonate, sodium hydrogen carbonate, sodium sulfate decahydrate, erythritol, xylitol, sorbitol, urea, taurine, glycine and the like. It is done. Among these, sodium chloride, sodium thiosulfate pentahydrate, chlorides such as ammonium sulfate, thiosulfate, and ammonium salts are preferable. These may be used alone or in combination of two or more.

  Other components that may be contained together with the water-soluble endothermic substance (a) include surfactants, water-insoluble minerals, water-soluble polymers, water-soluble salts, builders commonly used in the field of clothing detergents, and prevention of recontamination. Agents (carboxymethylcellulose) enzymes, fluorescent brighteners, foam suppressors (silicones, etc.), amorphous silica and amorphous aluminosilicates with high oil absorption, fragrances, soft detergent composite particles (clay minerals), etc. be able to.

  The endothermic particles (A) have an average particle size of preferably from 1 to 1200 μm, more preferably from 150 to 500 μm, more preferably from 150 to 450 μm, from the viewpoint of mixing with the exothermic particles (B) and solubility in the washing bath. More preferred is 180 to 400 μm. An average particle diameter is measured by the method as described in an Example.

[Pyrogenic particle (B) containing water-soluble pyrogen (b)]
The exothermic particles (B) contain a water-soluble exothermic substance (b) and other components as necessary. Since the exothermic particles (B) exhibit exothermic properties as a whole, they are included in the exothermic particles (B) as long as they exhibit exothermic properties as a whole even if they contain the water-soluble endothermic substance (a). It is. For example, when the water-soluble endothermic substance (a) is a particle obtained by a method other than granular mixing, for example, a slurry blended with other components and spray-dried, when it is dissolved in water, the entire particle generates heat. The particles exhibiting the property are exothermic particles (B).

  The water-soluble pyrogen (b) has a heat of dissolution in water of −150 to −1 kJ / mol, preferably −120 to −10 kJ / mol, more preferably −90 to −20 (kJ / mol). Is.

  Examples of the water-soluble pyrogen (b) include exothermic detergent particles, carbonates, sulfates, thiosulfates, sulfites, hydrogen sulfates, alkali metal salts such as hydrochlorides or phosphates, crystalline silicates, etc. Examples thereof include water-soluble inorganic salts such as silicate compounds, ammonium salts, and amine salts, and low-molecular weight water-soluble organic acid salts such as citrate and fumarate. Among these, carbonates such as sodium carbonate, sodium thiosulfate, potassium carbonate, sodium sulfate, and sodium sulfite, inorganic salt particles such as thiosulfate, and exothermic detergent particles are preferable. These may be used alone or in combination of two or more.

  For example, the exothermic detergent particles described above are a solid anionic surfactant neutralized product obtained by a dry neutralization method in which a neutralization reaction is performed with an acid precursor of an anionic surfactant and solid alkali particles. . When the dry neutralization method is used, there is an advantage that the equipment becomes compact because the spray drying process is not necessary. The neutralization method at the time of dry neutralization is not particularly limited, and neutralization may be performed by kneading / kneading, followed by crushing granulation, or neutralization reaction while applying shearing force in a stirring granulator May be performed.

  From the viewpoint of mixing with the endothermic particles (A) and solubility in the washing bath, the exothermic particles (B) preferably have an average particle size of 1-1200 μm, more preferably 150-500 μm, and 150-450 μm. More preferred is 180 to 400 μm. An average particle diameter is measured by the method as described in an Example.

  In the exothermic particles (B), other components that may be contained together with the surfactant and further the water-soluble exothermic substance (b) include water-insoluble inorganic substances, water-soluble polymers, water-soluble salts, and laundry detergents. Commonly used builders, bleach (percarbonate, perborate, bleach activator, etc.), recontamination inhibitor (carboxymethylcellulose, etc.), enzyme, reducing agent (thiosulfate, sulfite, etc.), fluorescence Examples thereof include a whitening agent, an antifoaming agent (silicone, etc.), amorphous silica and amorphous aluminosilicate having a high oil absorption capacity, a fragrance, and soft detergent composite particles (clay mineral). Among these, from the viewpoint of cleaning performance and production suitability, it is preferable to contain a surfactant, a poorly water-soluble inorganic substance, a water-soluble polymer, and a water-soluble salt.

Field Menkatsu agent is used in the present invention. Surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants.

  Examples of the anionic surfactant include sulfates of higher alcohols or ethoxylates thereof, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or ester salts thereof, fatty acid salts. Etc. In particular, linear alkylbenzene sulfonates having 10 to 18 (preferably 12 to 14) carbon atoms in the alkyl chain and α-sulfo fatty acid alkyl ester salts having 10 to 20 carbon atoms are preferred. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonia salts, alkanolamine salts and the like.

  Nonionic surfactants include, for example, ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. . In particular, an EO1 to 10 mol adduct of an alcohol having 10 to 16 carbon atoms is preferred from the viewpoint of removal of sebum soil, hard water resistance, biodegradability, and compatibility with linear alkylbenzene sulfonate.

  The content of the surfactant is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass from the viewpoints of production performance and foamability.

  In the present invention, a water-insoluble inorganic substance can generally be used in addition to the above components. The water-insoluble inorganic material preferably has an average primary particle size of 0.1 to 20 μm. Examples of the water-insoluble inorganic substance include crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite and bentonite. Among these, crystalline aluminosilicate is preferable from the viewpoint of sequestering ability and surfactant oil absorption ability.

  The content of the poorly water-soluble inorganic substance is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and still more preferably 15 to 30% by mass, from the viewpoint of particle strength and supporting force.

  In addition, water-soluble polymers and salts can be used as preferable components. Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Among these, carboxylic acid polymers having an average molecular weight of several thousand to 100,000 are preferable from the viewpoints of sequestering ability, dispersibility of solid dirt and particle dirt, and ability to prevent recontamination, and among them, acrylic acid-maleic acid copolymers. More preferred are salts and polyacrylates. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like.

  The content of the water-soluble polymer is preferably 2 to 15% by mass, more preferably 2 to 10% by mass, and still more preferably 3 to 8% by mass.

  Water-soluble salts include water-soluble salts such as carbonates, hydrogencarbonates, sulfates, thiosulfates, sulfites, hydrogensulfates, hydrochlorides, phosphates, and other alkali metal salts, ammonium salts, and amine salts. Examples thereof include inorganic salts and water-soluble organic salts having a low molecular weight such as citrate and fumarate.

  The content of the water-soluble salt is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 25 to 65% by mass.

[Other components that the detergent composition may contain]
In addition to the endothermic particles (A) and the exothermic particles (B), the detergent composition of the present invention includes a builder or bleach (percarbonate, perborate, Bleach activators, etc.), anti-contamination agents (carboxymethyl cellulose, etc.), enzymes, reducing agents (thiosulfates, sulfites, etc.), fluorescent brighteners, foam suppressors (silicone, etc.), non-oil with high oil absorption Crystalline silica, amorphous aluminosilicate, soft detergent composite particles (clay mineral), fragrance and the like can be contained.

  Examples of clay minerals include talc, pyrophyllite, smectite (saponite, hectorite, soconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, muscovite mica). , Paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, suedite, dombasite, etc.), brittle mica (clinentite, margarite, etc.), sulite, serpentine mineral (antigolite) , Lizardite, chrysotile, amicite, cronsteadite, burcherin, greenerite, garnierite, etc.), kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.). From a performance standpoint, talc, smectite, swelling mica, vermiculite, chrysotile, kaolin minerals and the like are preferable, smectites are more preferable, and montmorillonite is more desirable. These may be used alone or in appropriate combination of two or more.

  The content of the clay mineral in the composition is preferably 4 to 18% by mass, more preferably 5 to 16% by mass, further preferably 6 to 15% by mass, and 7 to 14% by mass from the viewpoints of softness and cleaning performance. Is particularly preferred.

  In the detergent composition of the present invention, the water content is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of storage stability.

  The detergent composition of the present invention is contained so that the mass ratio [(A) / (B)] of the endothermic particles (A) and the exothermic particles (B) is 0.05 to 4, and the mass ratio is , Preferably 0.1-3, more preferably 0.2-1.5.

<Method for producing detergent composition>
(1) First production method The detergent composition of the present invention can be obtained by mixing endothermic particles (A), exothermic particles (B), a surfactant, and, if necessary, other components. .
As the mixing method, the endothermic particles (A) and the exothermic particles (B) are a mixer equipped with stirring blades such as a drum mixer, a ribbon mixer, a Redige mixer, a high speed mixer, a Shugi mixer, a fluidized bed structure, etc. A fluid mixer such as a granulator or a granule bed granulator, a rolling mixer such as a drum mixer or a V-type mixer dish granulator can be used. Moreover, the method of mixing with a belt conveyor and an air transporter can also be used.

(2) Second production method The detergent composition of the present invention can also be obtained by a production method having the following steps. Hereinafter, it demonstrates for every process.

  First, in the first step, about 45 to 55 parts by mass of water is added to 100 parts by mass of the total amount of the water-soluble exothermic substance (b) and other components excluding the surfactant to obtain a slurry. .

  In the next step, the slurry obtained in the previous step is spray-dried to obtain base particles. In this step, a method of increasing the bulk density by applying agitation granulation method and rolling granulation method to particles with low bulk density obtained by spray drying or using a continuous kneader. A method of granulating by a mixing / extrusion method can also be added.

  In addition, instead of spray drying, granulation can be carried out by applying a mixing / extrusion method, but in that case, pulverization after extrusion is necessary for improving fluidity and appearance of particles. preferable.

  In the next step, the base particles obtained in the previous step are loaded with a surfactant or other components to be added as necessary to obtain exothermic particles (B). The method for supporting the surfactant on the base particles is not particularly limited. For example, the base particles and a liquid surfactant (one kind or a mixture of two or more kinds) may be batch-wise or continuous. It is possible to apply a method of charging to a mixer.

  The exothermic particles (B) obtained by such a second production method have an average particle size within the above range from the viewpoint of preventing dissolution delay due to pasting and the solubility of the exothermic particles (B) themselves. Is preferred.

  In the next step, the endothermic particles (A) and the exothermic particles (B) obtained in the previous step are mixed to obtain a detergent composition. In addition, from the viewpoint of improving the fluidity and non-caking property of the detergent composition, the surface modification may be performed by mixing a modifier such as inorganic fine powder. In this case, the average particle diameter of the modifier is preferably 0.1 to 20 μm.

  Examples of the surface modifier include silicate compounds such as aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound, water-soluble exothermic substance (b), metal Examples include soaps, fine powders such as powder surfactants, carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. When adding a fatty acid, it is preferable to neutralize with the alkali component in a detergent composition, and to become soap.

  In addition, the structure of the exothermic particles (B) obtained by the second production method is a structure in which more water-soluble polymers and / or water-soluble salts exist near the surface than inside the exothermic particles (B). Can be. The exothermic particles (B) exhibiting such uneven distribution exhibit a dissolution behavior in which water-soluble components near the surface are rapidly dissolved in water, thereby accelerating disintegration from the surface of the exothermic particles (B). Therefore, the exothermic particles (B) exhibit high-speed solubility and can obtain a detergent particle group excellent in solubility.

  The uneven distribution of the structure of the exothermic particles (B) can be confirmed by the following method. First, the exothermic particles (B) to be measured and the exothermic particles (B) pulverized product in which the exothermic particles (B) are sufficiently pulverized with an agate mortar or the like to prepare a uniform state are prepared. Then, under the condition that information at a depth of about 10 μm from the surface of the exothermic particles (B) can be obtained, both are combined with Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS). By this method (referred to as “FT-IR / PAS”), the uneven distribution of the structure of the exothermic particles (B) can be confirmed. This is a method of analyzing the distribution state of substances in the depth direction from the surface of the exothermic particles (B) as described in APPLIED SPECTROSCOPY vol.47, 1311-1316 (1993).

  The relative area intensity with respect to the characteristic peak of the water-insoluble inorganic salt when measured in a state where the uneven distribution structure is retained is the relative area intensity with respect to the characteristic peak of the water-insoluble inorganic salt when measured as a uniform state after grinding. The ratio is preferably 1.1 or more, more preferably 1.3 or more for water-soluble salts, and preferably 1.3 or more, more preferably 1.5 or more for water-soluble polymers.

  Preferred exothermic particles (B) are those capable of releasing bubbles having a diameter of 1/10 or more of the average particle diameter from the inside of the particles in the process of dissolving in water. In the process of dissolving such exothermic particles (B), first, when a small amount of water permeates into the particles, bubbles of a predetermined size are released from the inside of the particles, and then a large amount of particles are contained inside the particles. When the water permeates, the particles themselves collapse (self-collapse of the particles), and dissolution and collapse not only from the vicinity of the surface but also from the inside of the particles occur.

  Such dissolution behavior is preferably 1/10 or more, more preferably 1/5 or more, more preferably 1/5 or more of the average particle diameter of the exothermic particles (B) when the foam-releasing detergent particles are dissolved in water. The phenomenon of releasing bubbles having a diameter of 1/4 or more, particularly preferably 1/3 or more (hereinafter referred to as bubbles of a predetermined size) can be confirmed with a digital microscope, an optical microscope, or the like. The time from when the exothermic particles (B) are allowed to dissolve in water to the generation of bubbles of a predetermined size is preferably within 120 seconds, more preferably within 60 seconds, and within 45 seconds. Is more preferable.

  From the viewpoint of solubility, the exothermic particles (B) are preferably contained in an amount of 60% by mass or more, more preferably 80% by mass or more in the detergent composition.

  The bubble diameter is measured as follows. Attach a double-sided tape to the center of the bottom of the glass petri dish (inner diameter 50 mm). After depositing the exothermic particles (B) on the double-sided tape, the equivalent circle diameter (μm) of each of the exothermic particles (B) is measured from an image obtained using a digital microscope. As the digital microscope, for example, trade name: VH-6300 manufactured by KEYENCE Corporation can be used.

  Subsequently, 5 mL of ion-exchanged water at 20 ° C. is poured into the glass petri dish, and the dissolution behavior of the individual particles to be measured is observed. When bubbles are released from the inside of the particle, the equivalent circle diameter (α μm) of the bubble is measured from an image at the moment when the bubble leaves the particle. When a plurality of bubbles are released from the inside of the particle, the maximum circle equivalent diameter measured for each bubble is β μm. The ratio of the bubble diameter to the average particle diameter (β / α) is determined for each particle.

  In the preferred bubble-release detergent particles, it is preferable that pores having a diameter of 1/10 to 4/5, preferably 1/5 to 4/5 of the average particle diameter of the detergent particles are present inside the particles.

  The pore diameter can be measured as follows. Cut with a knife or the like on the surface containing the maximum particle size so as not to break the selected particles. When the cut surface is observed with a scanning electron microscope (SEM), the equivalent circle diameter (particle diameter) (γ μm) of the cut surface of the cut particles and the presence of pores inside the particles are confirmed. The pore diameter) (δμm) is measured. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore among them is δ μm. Then, the ratio of pore diameter to particle diameter (δ / γ) is determined.

  The detergent composition of the present invention contains an endothermic particle (A) containing a water-soluble endothermic substance (a) and an exothermic particle (B) containing a water-soluble exothermic substance (b). a) and a water-soluble exothermic substance (b) are contained in a predetermined ratio. For this reason, when the detergent composition is put in a lump in a washing bath having a low water temperature (10 ° C. or less or 5 ° C. or less), or after the detergent composition is put in a lump, the low water temperature (below 10 ° C. or 5 Even when water of less than or equal to (° C.) is injected, there is almost no undissolved residue of the components contained in the detergent composition, and a high detergency as in the contained components can be exhibited. The reason why such an action is performed is considered as follows.

  For example, in a conventional detergent, when cold water at 5 ° C. and a bulk detergent come into contact with each other, a water-soluble inorganic salt such as sodium carbonate melts in water and generates heat due to heat of fusion. Promoted. However, as a result of rapid cooling of the contact portion with the cold water, a continuous layer of hydrated crystals is formed on the surface of the lump, and the penetration of water into the interior is hindered. For this reason, it is thought that the undissolved residue of the detergent is generated as a result of the internal cooling.

  On the other hand, in the detergent composition of the present invention, for example, when cold water at 5 ° C. and a bulky detergent composition come into contact, the heat of fusion is suppressed by the cooperative action of the endothermic particles (A) and the exothermic particles (B). As a result, the formation of a continuous layer of hydrated crystals on the surface of the lump is suppressed. For this reason, water penetrates easily into the inside of the lump, generation of undissolved residue is reduced, and it is considered that high detergency by the original detergent component is exhibited.

  In addition, the detergent composition obtained by applying the above-described second production method is preferable because the above-described effect is exhibited more remarkably because the exothermic particles (B) have particularly good disintegration properties.

(Production of exothermic particles (B))
Water was added to a mixing tank having a stirring blade, and after the water temperature reached 55 ° C., sodium chloride (yaki salt, manufactured by Nippon Salt Co., Ltd.) and sodium sulfate were added. After stirring this for 15 minutes, sodium carbonate was added, and after completion of the addition, an aqueous sodium polyacrylate solution (average molecular weight of 15,000, manufactured by Kao Corporation) was added. This was further stirred for 15 minutes, and then zeolite [manufactured by Tosoh Corporation, trade name: 4A-type zeolite] was added. This was stirred for 30 minutes to obtain a slurry. The final temperature of this slurry was 60 ° C.

  This slurry was supplied to a spray drying tower, and sprayed from the top of the tower at a spraying pressure of 2,45 MPa to prepare base granule group 1. The composition of the obtained base granule group 1 was composed of 8% by mass of sodium chloride, 12% by mass of sodium polyacrylate, 28% by mass of sodium carbonate, 26% by mass of sodium sulfate, and 26% by mass of zeolite.

  Next, detergent particles were obtained by adding a surfactant or the like to the base granules 1. That is, an activator mixture at 70 ° C. composed of a nonionic surfactant, an anionic surfactant, polyethylene glycol and water was prepared. The composition was composed of 39% by mass of a nonionic surfactant, 46% by mass of an anionic surfactant, 2% by mass of polyethylene glycol and 13% by mass of water.

  Next, 36 parts by mass of the base granule group 1 was put into a Redige mixer (Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and stirring of the main shaft (100 rpm) was started. Thereto, 20 parts by mass of the above-mentioned activator mixture was added in 3 minutes, and stirred for 5 minutes. Further, 1 part by mass of palmitic acid [manufactured by Kao Corporation, trade name: LUNAC P-95] was added to this mixer in 30 seconds, and then stirred for 3 minutes. Further, 2 parts by mass of crystalline silicate, 24 parts by mass of soda ash, and 12 parts by mass of zeolite are put into this mixer, surface coating is performed, the detergent particles are classified using a sieve having an opening of 1180 μm, and particles less than 1180 μm are obtained. A group of detergent particles having a diameter was obtained.

  Next, 5 parts by mass of zeolite, 0.4 parts by mass of fragrance, and 0.4 parts by mass of enzyme (trade name: Cellulase K, manufactured by Novo Corp., trade name: Cannase 24TK, Novo, trade name: Sabinase 6.0T is used at a mass ratio of 3: 1: 2) is subjected to after-blending with a rotary kiln, and the detergent particles are classified using a sieve having an opening of 2000 μm. A group of detergent particles having a diameter was obtained. This was designated as exothermic particles (B).

(Measurement of average particle size)
It calculated | required using the sieve prescribed | regulated to JISZ8801. That is, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, and 125 μm, a low tap machine (made by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute), 100 g of the sample was vibrated for 10 minutes and sieved, and then the saucer and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm When the weight frequency is accumulated on the top, the opening of the first sieve where the accumulated weight frequency is 50% or more is aμm, and the opening of the sieve that is one step larger than aμm is bμm. When the weight frequency integrated up to the sieve is c% and the weight frequency on the aμm sieve is d%, Average particle size) = 10 ^A was determined from the following formula.

表１に示す粒子は、水溶性吸熱物質（ａ）である塩化ナトリウムが配合されているが、全体として発熱性を示すものであるから、発熱性粒子（Ｂ）となる。
・ＬＡＳ−Ｎａ：アルキル基の炭素数１２〜１４の直鎖アルキルベンゼンスルホン酸ナトリウム
・非イオン界面活性剤：炭素数１２〜１４の１級アルコールにＥＯを平均１２モル付加させたもの
・脂肪酸Na：アルキル基の炭素数が１０〜１８の脂肪酸ナトリウム
・ゼオライト：4A型ゼオライト（ゼオビルダー）
・炭酸ナトリウム：水溶性発熱物質（ｂ）
・結晶性シリケート：「プリフィード顆粒品」（株式会社トクヤマシルテック製）
・ＡＡポリマー：ポリアクリル酸（平均分子量１．５万；ＧＰＣによる測定、ポリエチレングリコール換算）
・ＰＥＧ：ポリエチレングリコール（平均重量分子量１０，０００）
・酵素：プロテアーゼ造粒物：花王社製「ＫＡＰ」・セルラーゼ造粒物：花王社製「ＫＡＣ」。

Although the particle | grains shown in Table 1 mix | blend sodium chloride which is a water-soluble endothermic substance (a), since it exhibits exothermicity as a whole, it becomes an exothermic particle (B).
LAS-Na: linear alkyl benzene sulfonate having 12 to 14 carbon atoms in the alkyl group Non-ionic surfactant: a mixture of primary alcohols having 12 to 14 carbon atoms with an average of 12 mol of EO fatty acid Na: Fatty acid sodium zeolite with 10-18 carbon atoms in the alkyl group: 4A type zeolite (Zeobuilder)
・ Sodium carbonate: water-soluble pyrogen (b)
・ Crystalline silicate: “Pre-feed granule” (manufactured by Tokuyama Siltech Co., Ltd.)
AA polymer: polyacrylic acid (average molecular weight 15,000; measured by GPC, converted to polyethylene glycol)
PEG: polyethylene glycol (average weight molecular weight 10,000)
・ Enzyme: Protease granulated product: “KAP” manufactured by Kao Corporation ・ Cellulase granulated product: “KAC” manufactured by Kao Corporation.

Examples and Comparative Examples The endothermic particles (A) and exothermic particles (B) shown in Table 2 were blended by hand for 15 seconds using a Unipack F bag to obtain a detergent composition. The obtained composition was subjected to the following tests.

(1) Low temperature solubility of composition-1 (paste formability, paste residual rate)
17.5 g of the detergent compositions shown in Tables 1 and 2 were put together in the assembled state near one outer periphery of the fan-shaped depression divided into six parts of the pulsator of the Matsushita Electric Industrial washing machine “Aizuma NA-F42Y1”.
Next, 22 L of tap water of 5 ° C. was poured at a flow rate of 10 L / min so that the detergent composition was not directly exposed to water, and left standing after the pouring was completed.
Five minutes after the end of pouring, stirring was started with a weak water flow (hand washing mode), and after stirring for 3 minutes, the water was drained, and the state of the detergent remaining in the washing tub was determined according to the following evaluation criteria. The “residual particle area” described below refers to the total area when the remaining detergent particles are spread in a container having a flat bottom.
[Evaluation criteria for paste formability]
(Double-circle): There is no aggregate or it cannot visually recognize.
A: Almost no aggregate (residual particle area within 25 mm ² ).
△: (100 mm ² within beyond residual particle area 25 mm ²⁾ which agglomerates remaining small amount.
X: Agglomerates remain in large quantities (residual particle area exceeds 100 mm ² )
[Paste residual rate]
The paste residual rate was calculated from the following formula.
Paste residual ratio (%) = (mass of composition at the time of charging−mass of the remaining composition) / mass of the composition at the time of charging × 100

(2) Low-temperature solubility of composition-2 (paste strength)
In a petri dish having an inner diameter of 5 cm and a height of 1.4 cm, 17.5 g of the detergent composition shown in Table 3 was weighed with a precision balance and placed in the petri dish. The composition surface in the petri dish was smoothed at the bottom of another petri dish (inner diameter 4.5 cm, mass 20 g).
Next, a petri dish containing the composition was placed in the vicinity of the center of a stainless steel pad 19 cm long, 23.5 cm wide and 3.5 cm high.
Next, 1 L of 5 ° C. replacement water was gently poured into the stainless steel pad so as not to enter the petri dish, and allowed to stand for 5 minutes.
5 minutes later, the petri dish containing the composition is taken out, and with a rheometer made by Rheotech, the tooth-shaped push rod A of a special adapter made by Rheotech is used to enter 1 cm from the surface of the composition in the petri dish. The penetration strength at that time was defined as the paste strength.
〔Evaluation criteria〕
A: When the paste strength is less than 100 g, B: Paste strength is 100 g or more but less than 120 g Δ: Paste strength is 120 g or more but less than 150 g X: Paste strength is 150 g or more

(3) Water permeability test A stainless steel 200 mesh is laid on the bottom near the center of a stainless steel pad 19 cm long, 23.5 cm wide and 3.5 cm high, and an opening surface of a glass tube with an inner diameter of 0.5 cm is placed on it. Standing vertically with respect to 200 mesh, it was fixed with a stand. The glass tube was filled with 1 g of the weighed composition. Exchange water at 5 ° C. was poured into the pad, the water penetration distance in the glass tube after 5 minutes was measured, and the penetration rate of cold water was determined from the following formula. The penetration rate of cold water was evaluated according to the following evaluation criteria.
Cold water penetration rate =
(Penetration distance of cold water of exothermic particles (B) −penetration distance of cold water of mixed particles (A) and (B)) / penetration distance of cold water of exothermic particles (B) × 100
◎: Cold water penetration rate of 10% or more ○: Cold water penetration rate of 5% or more to less than 10% △: Cold water penetration rate of 1% or more to less than 5% ×: Cold water penetration rate of 0% or less

(4) Measurement of wet calorific value (temperature drop rate of composition with respect to exothermic particles (B))
At room temperature (25 ° C.), 17.5 g of the detergent composition shown in Table 2 was weighed with a precision balance in a petri dish having an inner diameter of 5 cm and a height of 1.4 cm, and placed in the petri dish. The composition surface in the petri dish was smoothed at the bottom of another petri dish (inner diameter 4.5 cm, mass 20 g).
Next, a petri dish containing the composition was placed in the vicinity of the center of a stainless steel pad 19 cm long, 23.5 cm wide and 3.5 cm high.
Next, the thermocouple portion of the thermocouple type digital thermometer was fixed to the center portion of the petri dish containing the composition so as not to move with a stand. The temperature is measured for a while and the place where the temperature of the composition becomes constant is defined as t1.
Next, 1 L of ion exchange water at 5 ° C. is gently poured into the stainless steel pad so that it does not scatter in the composition in the petri dish, and water is poured into the petri dish until the ion-exchanged water enters the composition in the petri dish. Wet with 5 ° C. exchange water.
The maximum temperature change of the composition in the petri dish was measured, and this was set as the maximum temperature t2, and the maximum temperature generated by the hydration reaction was determined. The value obtained by dividing the difference between the maximum temperature of the composition and the exothermic particles (B) by the maximum temperature of the exothermic particles (B) was defined as the temperature drop rate. The temperature drop rate was evaluated according to the following evaluation criteria.
Temperature drop rate (%) of composition relative to exothermic particles (B) = (maximum temperature after wetting exothermic particles (B) −maximum temperature after wetting of mixed particles (A) and (B)) / exothermic property Maximum temperature after wetting of particles (B) × 100
〔Evaluation criteria〕
A: Temperature drop rate of the composition with respect to the exothermic particles (B) is 25% or more. B: Temperature drop rate of the composition with respect to the exothermic particles (B) is 10% to less than 25%. Δ: Exothermic particles (B) The temperature drop rate of the composition relative to the exothermic particles (B) is 0% or less.

Endothermic particles (A)
・ Sodium chloride (Kishida Chemical reagent), heat of dissolution 3.883 (kJ / mol), average particle size 575μm
・ Sodium thiosulfate pentahydrate (Kanto Chemical Reagent), heat of solution 47.3 (kJ / mol), average particle size 912μm
Ammonium sulfate (Wako Pure Chemicals reagent), heat of dissolution 6.57 (kJ / mol), average particle size 478μm
Exothermic particles (B)
・ Anhydrous sodium carbonate (Wako Pure Chemicals Reagents), heat of dissolution-26.7 (kJ / mol), average particle size 436μm
-Particles of Production Example 1: Average particle size 250-350 μm, heat generation temperature Δt 5 ° C.-10 ° C.

Claims (4)

A detergent composition comprising an endothermic particle (A) containing a water-soluble endothermic substance (a), an exothermic particle (B) containing a water-soluble exothermic substance (b), and a surfactant,
The water-soluble endothermic substance (a) is selected from sodium thiosulfate pentahydrate and ammonium sulfate, and the water-soluble exothermic substance (b) is selected from sodium carbonate and sodium thiosulfate,
The endothermic particles (A) have an average particle size of 1 to 1200 μm, and the exothermic particles (B) have an average particle size of 1 to 1200 μm,
The detergent composition contained so that mass ratio [(A) / (B)] of the said endothermic particle (A) and the said exothermic particle (B) may be 0.05-4. The detergent composition according to claim 1, wherein the water-soluble endothermic substance (a) is sodium thiosulfate pentahydrate and the water-soluble exothermic substance (b) is sodium carbonate. The detergent composition according to claim 1 or 2 , wherein the exothermic particles (B) contain the water-soluble exothermic substance (b) and at least a surfactant. It is a manufacturing method of the detergent composition according to any one of claims 1 to 3 ,
A step of obtaining a slurry comprising the water-soluble exothermic substance (b) and other components blended as necessary;
Spray drying the slurry to obtain base particles;
A step of loading the base particles with a surfactant to obtain exothermic particles (B);
Mixing the endothermic particles (A) and the exothermic particles (B);
And the other component contains a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt .