JP2013256594A - Particle for adding detergent and granular detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide particles for adding a detergent, with which the solubility and suppressing effect on solidification of a granular detergent are further improved.SOLUTION: Particles for adding a detergent are composed of a granulated substance which is constituted of a component (A): particles of an alkali metal sulfate, a component (B): particles of an alkali metal hydrogen carbonate, and a component (C): a binder, wherein a ratio represented by [average particle size of particles to be compounded of the component (B)]/[average particle size of particles to be compounded of the component (A)] is 0.3 or less. It is desirable that the component (B) adhere to a surface of the component (A).

Description

  The present invention relates to a detergent additive particle and a granular detergent.

In recent years, attempts have been made to reduce the surfactant content of granular detergents for clothing and the like from the viewpoint of environmental considerations. And in order to prevent the detergency from deteriorating due to the reduction of the surfactant content in the granular detergent, and to further improve the detergency, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonate It is known to add inorganic salts such as potassium hydrogen.
Examples of the method for adding the inorganic salt to the granular detergent include a method in which a slurry liquid containing an inorganic salt and a surfactant is spray-dried to obtain spray-dried particles. For example, the method of mixing the spray-drying particle | grains or granulated cleaning agent particle | grains containing surfactant, and an inorganic salt is mentioned. Further, for example, a method of granulating spray-dried particles or granulated detergent particles containing a surfactant and an inorganic salt can be mentioned.
When cleaning is performed using a cleaning liquid in which the granular cleaning agent thus obtained is dispersed in water, there is a problem that inorganic salts form aggregates in the cleaning liquid and are difficult to dissolve in water (insolubilization). This insolubilization becomes more prominent as the blending amount of the inorganic salt increases or the water temperature decreases.
In order to solve this problem, a cleaning composition containing a specific ratio of endothermic particles containing a water-soluble endothermic substance, exothermic particles containing a water-soluble exothermic substance, and a surfactant has been proposed (for example, Patent Document 1). According to the invention of Patent Document 1, improvement in solubility and dispersibility at a low water temperature is achieved.

In addition, depending on the type of the inorganic salt, there is a problem that the granular cleaning agent is easily solidified during storage.
In order to solve this problem, detergent addition particles in which the surfaces of granulated particles of sodium sulfate, water-soluble inorganic potassium salt, polycarboxylate and water are coated with water-soluble inorganic powder have been proposed (for example, patents). Reference 2). According to the invention of Patent Document 2, the solubility in water (hereinafter sometimes simply referred to as solubility) and the solidification suppression effect during storage (hereinafter simply referred to as solidification suppression effect) and Is planned.

JP 2009-161606 A JP 2010-195892 A

However, granular detergents containing inorganic salts are required to have further improved solubility and improved solidification suppression effect. In addition, while there is a desire to further increase the amount of inorganic salt, simply increasing the amount of inorganic salt makes the resulting granular detergent difficult to dissolve in water and easily solidifies during storage. There is a tendency.
Then, this invention aims at the particle | grains for detergent addition which can improve the solubility and solidification inhibitory effect of a granular detergent more.

The detergent additive particles of the present invention are a granulated product of (A) component: alkali metal sulfate particles, (B) component: alkali metal hydrogen carbonate particles, and (C) component: binder. And the ratio represented by [average particle diameter of the particle group of the component (B) to be blended] / [average particle diameter of the particle group of the component (A) to be blended] is 0.3 or less. It is characterized by that.
The component (B) is preferably attached to the surface of the component (A).

  The granular cleaning agent of the present invention is characterized in that the particles for adding the cleaning agent of the present invention are blended.

  According to the particles for adding a cleaning agent of the present invention, the solubility of the granular cleaning agent and the solidification suppressing effect can be improved.

(Granular detergent)
The granular cleaning agent of the present invention contains particles for adding a cleaning agent to be described later, and the particles for adding a cleaning agent exist as independent particles.

The bulk density of granular detergent is not particularly limited, for example, 0.6 g / cm ³ or more, more preferably 0.7 to 1.2 g / cm ^3, is 0.8~1.2g / cm ³ Further preferred. If it is at least the above lower limit value, there is little dusting and handling is easy, and if it is at most the above upper limit value, the solubility is better.
The bulk density is a value measured according to JIS-K3362.

  Although the average particle diameter of a granular cleaning agent is not specifically limited, 200-1500 micrometers is preferable, 250-1000 micrometers is more preferable, 300-700 micrometers is especially preferable. If it is at least the above lower limit value, there is little dusting and handling is easy, and if it is at most the above upper limit value, the solubility is better.

 The average particle diameter is measured by a classification operation using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a small sieve sieve is stacked on a tray in the order of a large sieve sieve, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, the lid is capped, and a low-tap sieve shaker (stock) (Made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, Measure the mass. Then, when the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “ bμm ”, the integrated value of the mass frequency from the tray to the aμm sieve is“ c% ”, and the mass frequency on the aμm sieve is“ d% ”. % Particle diameter) is determined and used as the average particle diameter of the sample.

  The pH of the granular detergent is not particularly limited, but from the viewpoint of enhancing the detergency, the 1% by weight aqueous solution of the granular detergent is preferably pH 8 or more, and more preferably pH 9-11.

<Cleaning agent addition particles>
The detergent additive particles of the present invention are a granulated product of (A) component: alkali metal sulfate particles, (B) component: alkali metal hydrogen carbonate particles, and (C) component: binder. It is.
The form of the particles for adding the detergent is not particularly limited, but the surface of the component (A) is coated with the component (B) via the component (C), and the surface of the component (A) is (B) to ( The particles in which the component (B) is attached to the surface of the component (A), such as those in which the component C) is mixed, or particles in which the components (A) to (C) are mixed may be used. From the viewpoint of further improving the solubility of the granular detergent and the effect of suppressing solidification, particles having the component (B) attached to the surface of the component (A) are preferable.

Although the bulk density of the particle group of the particles for adding detergent is not particularly limited, for example, 0.6 g / cm ³ or more is preferable, 0.7 to 1.2 g / cm ³ is more preferable, and 0.8 to 1. 2 g / cm ³ is more preferable. If it is more than the said lower limit, there is little powdering and handling is easy, and if it is below the said upper limit, the solubility of a granular cleaning agent is more favorable.

  The average particle size of the particle group of the detergent additive particles is not particularly limited, but is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 250 to 700 μm. If it is more than the said lower limit, there is little powdering and handling is easy, and if it is below the said upper limit, the solubility of a granular cleaning agent is more favorable.

 The content of the detergent-adding particles in the granular detergent can be determined in consideration of the detergency required for the granular detergent, for example, preferably 5% by mass or more, more preferably 10-30% by mass, and more preferably 15-15%. 25 mass% is further more preferable. If it is more than the said lower limit, the further improvement of a solubility and a solidification inhibitory effect can be aimed at, and if it is below the said upper limit, the mixing | blending balance with the cleaning agent arbitrary component mentioned later will become favorable, and the further improvement of a cleaning power can be aimed at.

<< (A) component: particles of alkali metal sulfate >>
The component (A) is alkali metal sulfate particles. While the component (A) enhances the cleaning power of the granular cleaning agent, it tends to remain undissolved in the cleaning liquid, causing a decrease in solubility.
Examples of the component (A) include sodium sulfate particles and potassium sulfate particles. Among them, sodium sulfate particles are preferable from the viewpoint of further improving the cleaning power of the granular detergent.

 200-1000 micrometers is preferable, as for the average particle diameter of the particle group of the (A) component mix | blended, 200-500 micrometers is more preferable, and 200-350 micrometers is more preferable. If it is less than the above lower limit, the solidification inhibitory effect of the granular detergent may be reduced, and if it exceeds the upper limit, the solubility of the granular detergent may be reduced.

 Although content of (A) component in the particle | grains for detergent addition is not specifically limited, 50 mass% or more is preferable, 50-94.9 mass% is more preferable, 85-90 mass% is further more preferable. If the amount is less than the lower limit, the solidification suppressing effect may be reduced. If the amount exceeds the upper limit, the component (B) may be too small to sufficiently increase the solubility of the granular cleaning agent.

<< (B) component: particles of alkali metal hydrogen carbonate >>
The component (B) is alkali metal hydrogen carbonate particles. While the component (B) enhances the solubility of the component (A), the presence of moisture tends to cause the components (B) to aggregate together, causing the granular detergent to solidify.
(B) As a component, sodium hydrogencarbonate particle | grains, potassium hydrogencarbonate particle | grains, etc. are mentioned, From a viewpoint of aiming at the further improvement of solubility, sodium hydrogencarbonate particle | grains are preferable especially.

  The average particle diameter of the particle group of the component (B) to be blended is, for example, preferably 10 to 100 μm, and more preferably 25 to 50 μm. If the amount is less than the above lower limit value, powdering is easy and handling is complicated, and if the value exceeds the upper limit value, it is difficult to granulate the detergent additive particles.

 The B / A particle size ratio represented by [average particle size of particle group of component (B) to be blended] / [average particle size of particle group of component (A) to be blended] is 0.3 or less. Yes, 0.05 to 0.3 is preferable, and 0.1 to 0.2 is more preferable. When the B / A particle size ratio exceeds the above upper limit, the (B) component that is not granulated together with the (A) component or the (C) component increases, and the (B) component aggregates to solidify the granular detergent. It becomes easy to do. If the B / A particle size ratio is less than the above lower limit, when the components (A) to (C) are granulated, the component (B) becomes a spatter and the solubility of the granular detergent decreases. There is a fear.

 5 mass% or more is preferable, as for content of (B) component in the particle | grains for detergent addition, 5-30 mass% is preferable, and 8-14.5 mass% is more preferable. If the amount is less than the above lower limit value, the solubility of the granular detergent may be lowered, and if the amount exceeds the upper limit value, the solidification suppressing effect of the granular detergent may be lowered.

 80 to 99.9 mass% is preferable and, as for the total amount of (A) component and (B) component in the particle | grains for detergent addition, 95 to 99.5 mass% is more preferable. If it is less than the said lower limit, the compounding effect of (A) component and (B) component will be hard to be exhibited, and if it exceeds the said upper limit, it may become difficult to granulate.

 In the detergent addition particles, the mass ratio represented by the component (B) / component (A) (hereinafter sometimes referred to as B / A mass ratio) is preferably 0.05 to 0.6, and 0.09. -0.17 is more preferable. If the B / A mass ratio is less than the above lower limit value, the solubility of the granular detergent may be lowered, and if it exceeds the upper limit value, the solidification suppressing effect of the granular detergent may be lowered.

≪ (C) component: Binder≫
Component (C) is a binder. Examples of the component (C) include surfactants such as anionic surfactants and nonionic surfactants, and glycols such as polyethylene glycol and polypropylene glycol. Among these, from the viewpoint of further improving detergency, anions Surfactants and nonionic surfactants are preferred. (C) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The anionic surfactant is not particularly limited as long as it has a function as a binder, and examples thereof include the following.
(1) A linear or branched alkylbenzene sulfonate (LAS salt or ABS salt) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 to Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 10 moles.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), average 3 to 30 mol An alkyl (or alkenyl) phenyl ether sulfate having an added linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 to An alkyl (or alkenyl) ether carboxylate having 10 to 20 carbon atoms and a linear or branched alkyl (or alkenyl) group added.
(8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(11) A fatty acid methyl ester sulfonate (MES salt) having 14 to 18 carbon atoms.
(12) A higher fatty acid salt (soap) having 10 to 20 carbon atoms.
These anionic surfactants can be used as alkali metal salts such as sodium salts and potassium salts, amine salts and ammonium salts. Moreover, these anionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

The nonionic surfactant is not particularly limited as long as it has a function as a binder, and examples thereof include the following.
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 5 to 20 moles of 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. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(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.

  Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the following general formula (31).

R ⁹ CO (OA) _q R ¹⁰ (31)

[In the formula (31), R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an addition unit (oxyalkylene group) of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and ethylene oxide, propylene oxide and the like are preferable. q shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is 5-20.
R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent. ]

  These nonionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

 Content of (C) component in the particle | grains for detergent addition can be suitably determined in consideration of a kind etc., for example, 0.1-5 mass% is preferable and 0.5-3 mass% is more preferable. If it is less than the above lower limit value, it tends to be difficult to granulate the detergent additive particles, and if it exceeds the above upper limit value, the adhesiveness of the surface of the detergent additive particles becomes too high to suppress solidification of the granular detergent. When the effect is reduced, or when dissolved in water, it partially gels and the solubility of the granular detergent may be reduced.

≪Optional components of detergent additive particles≫
The particles for adding a detergent may contain an optional component other than the components (A) to (C) (hereinafter sometimes referred to as an optional particle component). Examples of the particle arbitrary component include inorganic builders (arbitrary inorganic builders) other than the components (A) to (B).
Content of the particle | grain arbitrary component in the particle | grains for washing | cleaning agent addition is suitably determined in consideration of a kind etc. in the range which does not impair the effect of this invention.

The optional inorganic builder may be anything other than the components (A) to (B), for example, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite. Crystalline alkali metal silicate and amorphous alkali metal silicate such as salt, crystalline layered sodium silicate (for example, trade name [Na-SKS-6] (δ-Na ₂ O · 2SiO ₂ ) manufactured by Clariant Japan) Examples thereof include salts, alkali metal chlorides such as sodium chloride and potassium chloride, and aluminosilicates.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, zeolite can be suitably blended, and any of A type, X type, Y type, and P type can be used as the zeolite.

≪Method for producing detergent additive particles≫
The method for producing the detergent additive particles of the present invention is only required to granulate the components (A) to (C). For example, the components (A) to (C) are mixed to obtain a kneaded product. (Granulation and pulverization granulation method), (A) to (C) components are stirred and mixed while stirring (granulation method), (A) to (A) to (A) to (A) to (C) Examples thereof include a method of granulating the component (C) while rolling and mixing (rolling granulation method). Among them, the stirring granulation method or the rolling granulation method is preferable. If it is a stirring granulation method or a rolling granulation method, it will be easy to obtain the particle | grains which (B) component adhered to the surface of (A) component.

(1) Kneading and pulverizing granulation method The kneading and pulverizing granulation method, for example, kneads components (A) to (C) in advance with a mixing device (kneading operation), and uses the obtained kneaded product. A method of pulverizing (pulverizing operation) can be mentioned.
Examples of the mixing apparatus used for the kneading operation include a batch kneader and a continuous kneader.
In the kneading operation, the order of adding the components (A) to (C) is not particularly limited. For example, the components (A) to (B) are previously charged in a batch kneader and mixed, and then (C ) Component is added and further mixed and kneaded. In addition, for example, there is a method in which the component (C) is previously charged in a batch kneader, components (A) to (B) are added thereto, mixed and kneaded. Alternatively, a method of mixing and kneading while simultaneously supplying the components (A) to (C) to a continuous kneader can be mentioned.

(2) Stirring granulation method As stirring granulation method, for example, (C) stirring (A) component and (B) component with stirring granulators, such as a Redige mixer (made by Matsubo Co., Ltd.), (C ) Component addition method.
Examples of the method for adding the component (C) include a method of dropping or spraying the molten component (C) or an aqueous dispersion containing the component (C) (hereinafter sometimes referred to as a binder solution). It is done.
The temperature of the binder liquid to be added is appropriately determined according to the type of the component (C) and the like, and is preferably 30 to 75 ° C, for example. If it is more than the said lower limit, since fluidity | liquidity will be maintained and it will become easy to spread uniformly, the particle | grains for detergent addition can be manufactured stably. If the value exceeds the upper limit, decomposition of the component (B) may be promoted, and the content of the component (B) may be reduced.

(3) Rolling granulation method As the rolling granulation method, for example, the component (C) is allowed to flow while the component (A) and the component (B) are flowed in a mixing apparatus such as a container rotating cylindrical mixer. The method of adding is mentioned.
Examples of the method for adding the component (C) include a method in which a binder liquid is dropped or sprayed.
In the rolling granulation method, the temperature of the binder liquid added is the same as the temperature of the binder liquid added in the stirring granulation method.

<Optional components of granular detergent>
The granular detergent may contain optional components other than the detergent-adding particles (hereinafter sometimes referred to as “cleaner optional components”).
As detergent optional components, surfactant-containing particles, bleaching components, organic peracid precursors, metal compounds, sequestering agents, fragrances, dyes, fluorescent whitening agents, enzymes, enzyme stabilizers, anti-staining agents, Examples include an anti-caking agent, an antifoaming agent, a reducing agent, and a pH adjusting agent.

≪Surfactant-containing particles≫
The surfactant-containing particles are particles containing a surfactant and contribute to the improvement of the cleaning power of the granular cleaning agent.
The bulk density of the detergent containing particles, 0.5 g / cm ³ greater are preferred, more preferably 0.6~1.0g / cm ^3, more preferably 0.7~0.9g / cm ^3.

 The water content of the surfactant-containing particles is, for example, preferably 9% by mass or less, more preferably 6% by mass or less, and may be 0% by mass. If it is below the said upper limit, the further improvement of the solidification suppression effect of a granular cleaning agent can be aimed at.

Examples of the surfactant contained in the surfactant-containing particles include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, from the viewpoint of further improving detergency , Anionic surfactants and nonionic surfactants are preferred, anionic surfactants are more preferred, and MES salts are more preferred. These surfactants may be used singly or in combination of two or more.
The anionic surfactant contained in the surfactant-containing particles is the same as the anionic surfactant of the component (C), and the nonionic surfactant contained in the surfactant-containing particles is the nonion of the component (C). It is the same as the surfactant.

 The content of the surfactant in the surfactant-containing particles is determined in consideration of the type and the like, for example, preferably more than 5% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass. .

 The surfactant-containing particles may contain components other than the surfactant. Examples of components that the surfactant-containing particles may contain include detergency builders such as inorganic builders and organic builders.

As an inorganic builder, the above-mentioned arbitrary inorganic builder, (A) component, (B) component, etc. are mentioned.
The content of the inorganic builder in the surfactant-containing particles is determined in consideration of the type and the like, and is preferably 40 to 75% by mass, and more preferably 50 to 65% by mass. If it is less than the lower limit, it is difficult to obtain the blending effect of the inorganic builder, and if it exceeds the upper limit, the surfactant content is too small, and the cleaning power of the granular cleaning agent may be reduced.

  Examples of organic builders include hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, and gluconate; cyclocarboxylates such as pyromellitic acid, benzopolycarboxylate, and cyclopentanetetracarboxylate; Ether carboxylates such as carboxymethyl tartronate, carboxymethyl oxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; polyacrylates, salts of acrylic acid-allyl alcohol copolymers, acrylic acid-maleic acid copolymers Salt of polymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid; salt of acrylic acid polymer or copolymer such as hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer; maleic acid, itaconic acid, fumaric acid Acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, Polymers or copolymers of salts such as aspartic acid; starch, cellulose, amylose, polysaccharides derivatives such as polysaccharides oxides pectin etc., and the like. Of these, citrate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A No. 54-52196) are suitable.

  The content of the organic builder in the surfactant-containing particles is determined in consideration of the type thereof, and is preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass. If the amount is less than the lower limit, it is difficult to obtain the organic builder blending effect. If the amount exceeds the upper limit, the surfactant content is too low, and the cleaning power of the granular detergent may be reduced.

  A detergency builder may be used individually by 1 type, and 2 or more types may be used in combination. For the purpose of improving the cleaning effect and stain dispersibility in the cleaning solution, it is preferable to use an organic builder such as polyacrylate and a salt of acrylic acid-maleic acid copolymer and an inorganic builder such as zeolite.

 50-90 mass% is preferable, for example, and, as for content of surfactant-containing particle | grains in a granular cleaning agent, 60-85 mass% is more preferable.

  In the granular detergent, the mass ratio represented by the surfactant-containing particles / the detergent addition particles (hereinafter sometimes referred to as particle blending ratio) is preferably 1.7 to 9, and preferably 2.4 to 5.7. Is more preferable. If it is less than the said lower limit, surfactant may decrease too much and there exists a possibility that a detergency may fall. If the value exceeds the upper limit, there are too few particles for adding the cleaning agent, and the distribution in the granular cleaning agent is biased, which may reduce the cleaning power of the granular cleaning agent.

  As a method for producing the surfactant-containing particles, for example, a spray-drying slurry in which a surfactant is dispersed in water is spray-dried to obtain spray-dried particles, and the spray-dried particles and other raw materials are kneaded. And a method of kneading the surfactant and other raw materials and crushing them.

≪Bleach ingredient≫
Examples of the bleaching component include compounds that generate hydrogen peroxide in water. Examples of such a bleaching component include inorganic peroxides such as sodium percarbonate particles, sodium perborate particles, and sodium perborate trihydrate particles. The inorganic peroxide is, for example, a surface coated with silicic acid and / or silicate and boric acid and / or borate, or a surface coated with a surfactant such as LAS and an inorganic compound. It may be a coated peroxide particle such as an iron.

≪Organic peracid precursor≫
As the organic peracid precursor, conventionally known ones are used, and examples thereof include decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, and the like. An organic peracid precursor may be used individually by 1 type, and 2 or more types may be used in combination.

≪Metal salt≫
As the metal salt, conventionally known ones are used, for example, manganese compounds such as manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, manganese acetylacetonate; copper nitrate, copper sulfide, copper sulfate, Copper compounds such as copper chloride, copper acetate, copper cyanide, ammonium chloride, copper gluconate, copper tartrate, copper perchlorate; zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, chloride Examples thereof include zinc compounds such as ammonium zinc, zinc gluconate, zinc tartrate, and zinc perchlorate. A metal salt may be used individually by 1 type, and 2 or more types may be used in combination.

≪Metal ion sequestering agent≫
As the sequestering agent, conventionally known sequestering agents are used, and aminocarboxylic acids such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate. Aminocarboxylic acid type sequestering agents such as salts, serine diacetate, hydroxyiminodisuccinate, hydroxyaminocarboxylate such as hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; 1-hydroxyethane-1,1 -Diphosphonic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic Acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methyl) Phosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and other organic phosphonic acid derivatives or salts thereof; Examples thereof include organic acids such as diglycolic acid, tartaric acid, oxalic acid and gluconic acid, or salts thereof. Among these, the activity of the bleaching component can be further enhanced by using the aminocarboxylic acid type sequestering agent in combination with the above metal salt. One sequestering agent may be used alone, or two or more sequestering agents may be used in combination.

≪Perfume≫
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) consisting of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc. As this fragrance | flavor, the thing as described in Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2003-89800 etc. can be used, for example. A fragrance | flavor may be used individually by 1 type and may be used in combination of 2 or more type.

≪Dye≫
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, pigments are preferred, and compounds having oxidation resistance such as oxides are particularly preferred. Such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like. A pigment | dye may be used individually by 1 type, and 2 or more types may be combined and used for it.

≪Fluorescent whitening agent≫
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- ( Examples thereof include fluorescent whitening agents such as styrylphenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives. As the fluorescent brightening agent, one kind may be used alone, or two or more kinds may be used in combination.

≪Enzyme≫
The enzymes are classified according to the reactivity of the enzymes, and include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable. An enzyme may be used individually by 1 type and may be used in combination of 2 or more type.

≪Enzyme stabilizer≫
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. An enzyme stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

≪Recontamination inhibitor≫
Examples of the anti-staining agent include cellulose derivatives such as carboxymethylcellulose and hydroxypropylmethylcellulose. A recontamination inhibitor may be used individually by 1 type, and 2 or more types may be used in combination.

≪Anti-caking agent≫
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like. The anti-caking agent may be used alone or in combination of two or more.

≪Reducing agent≫
Examples of the reducing agent include sodium sulfite and potassium sulfite.

≪pH adjuster≫
Examples of the pH adjuster include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, alkali agents such as sodium hydroxide and potassium hydroxide, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, and lactic acid. And acid agents such as succinic acid, malic acid, gluconic acid or their polycarboxylic acids, sulfuric acid, and hydrochloric acid. A pH adjuster may be used individually by 1 type, and 2 or more types may be used in combination.

(Production method of granular detergent)
Examples of the method for producing the granular cleaning agent of the present invention include a method of powder-mixing cleaning agent-added particles and optional cleaning agent components such as surfactant-containing particles.
Also, for example, as a method for producing a granular detergent, surfactant-containing particles and granular detergent optional components such as a bleaching component and an organic peracid precursor are powder-mixed, and then a fragrance, a pigment, etc. A liquid cleaning agent optional component may be added and mixed, and cleaning agent addition particles may be added and mixed therewith.

(how to use)
As a method for cleaning an object to be washed using a granular detergent, for example, a washing liquid having a granular detergent concentration of 0.02 to 2% by mass is used to wash the article to be washed in a washing machine or to cover the washing liquid. A conventionally well-known washing method, such as soaking a washing thing, is mentioned.
Examples of the articles to be washed include textiles such as clothing, fabrics, curtains, and sheets.

  According to the particles for detergent addition of the present invention, since it is a granulated product of components (A) to (C) and the A / B particle size ratio is 0.3 or less, the solubility of the granular detergent and The solidification suppressing effect can be further enhanced.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, content or compounding quantity of each component in a table | surface represents the amount equivalent to a pure part.
(Raw materials used)
<Component (A): Alkali Metal Sulfate Particles>
A-1: Sodium sulfate particles. Neutral anhydrous sodium sulfate AO (manufactured by Shikoku Kasei Co., Ltd.) is screened and adjusted to an average particle size of 255 μm.

<(B) component: particles of alkali metal hydrogen carbonate>
B-1: Sodium hydrogen carbonate particles. Sodium hydrogen carbonate (Asahi Glass Co., Ltd.) is sieved and the average particle size is adjusted to 33.2 μm.
B-2: Sodium hydrogen carbonate particles. Sodium hydrogen carbonate (Asahi Glass Co., Ltd.) is sieved and the average particle size is adjusted to 20.4 μm.
B-3: Sodium hydrogen carbonate particles. Sodium hydrogen carbonate (Asahi Glass Co., Ltd.) is sieved and the average particle size is adjusted to 63.8 μm.
B-4: Sodium hydrogen carbonate particles. Sodium bicarbonate (Asahi Glass Co., Ltd.) was crushed with a stud mill type 63C (Ashino Sangyo Co., Ltd.) and adjusted to an average particle size of 12.8 μm.
B-5: Sodium hydrogen carbonate particles. Sodium hydrogen carbonate (Asahi Glass Co., Ltd.) is sieved and the average particle size is adjusted to 127.4 μm.

<(C) component: binder>
C-1: Nonionic surfactant. ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms, manufactured by Ecogreen Oleochemicals) with an average of 15 moles of ethylene oxide added. Made by Lion Corporation.

<Particle optional component>
Type A zeolite: Thai silicate (pure content 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.).

<Detergent optional component>
Surfactant-containing particles: those produced by the following production examples.

<< Production Example >> Method for Producing Surfactant-Containing Particles 1.3 parts by mass of linear alkylbenzene sulfonic acid, 10.7 parts by mass of A-type zeolite, 2.9 parts by mass of acrylic acid-maleic acid copolymer salt, sodium carbonate 43.1 parts by mass, 6.9 parts by mass of potassium carbonate, 20.3 parts by mass of sodium sulfate, 7.6 parts by mass of soap, and 0.5 parts by mass of 48% by mass aqueous potassium hydroxide solution were charged into the reactor. A slurry for spray drying having a solid content concentration of 60% by mass was prepared by dispersing in water. The reactor has a stirrer and a jacket, and the jacket temperature was set to 75 ° C. when preparing the slurry for spray drying.
Next, the slurry for spray drying is spray-dried under the following drying conditions in a countercurrent drying tower, and 2 parts by mass of zeolite A as a spray-dried particle coat coating agent is introduced from the lower part of the spray-drying tower to form spray-dried particles. Obtained. The obtained spray-dried particles had the composition shown in Table 1, and had an average particle diameter of 300 μm and a bulk density of 0.3 g / cm ³ .

[Drying conditions]
Spray drying apparatus: countercurrent type, tower diameter 2.0 m, effective length 5.0 m.
・ Atomization method: Pressure nozzle method.
-Spray pressure: 30 kg / cm < ² >.
-Hot air inlet temperature: 250 degreeC.
-Hot air outlet temperature: 100 ° C.

 The water content (% by mass) in the spray-dried particles is a value measured at 170 ° C. for 20 minutes using a Kett moisture meter (infrared moisture meter, manufactured by Kett Scientific Laboratory Co., Ltd.).

Continuous kneader (73.8 parts by weight of spray-dried particles, 17 parts by weight of fatty acid methyl ester sulfonate-containing paste, 1.4 parts by weight of nonionic surfactant, 0.2 parts by weight of fluorescent agent, and 1.1 parts by weight of water) KRC-S4 type (manufactured by Kurimoto Corporation) and kneaded (kneader rotation speed 135rpm, jacket inlet temperature 5 ° C, jacket outlet temperature 25 ° C (cooled by passing water through the jacket)) A koji product was prepared. The temperature of the obtained kneaded product was 55 ± 15 ° C.
Next, the kneaded product is put into a pelleter double (Fuji Paudal Co., Ltd., product name: EXD-100 type) and cut while being extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm (cutter peripheral speed: 5 m / s). ), A pellet-shaped molded body (diameter of about 10 mm, length of 70 mm or less (substantially 5 mm or more)) was obtained.

Fitzmill (made by Hosokawa Micron Co., Ltd., DKA-6) was added in 93.5 parts by mass of pellet-shaped compacts and 6.5 parts by mass of A-type zeolite as a grinding aid were placed in series in the presence of air. Type | mold), it grind | pulverized on the following grinding | pulverization conditions, and obtained surfactant-containing particle | grains. The temperature of the obtained surfactant-containing particles was 30 ± 10 ° C., the average particle size was 350 μm, the amount of particles having a particle size of 150 μm or less was 10% by mass, and the bulk density was 0.85 g / cm ³ .

[Crushing conditions]
-Air temperature: 15 ± 3 degreeC.
・ Blowing rate (ratio of gas / solid): 2.8 ± 0.25 m ³ / kg.
Screen diameter: 3 steps from top, 6mm, 4mm and 2mm.
・ Crusher rotation speed: 100% = 4700 rpm (circumferential speed about 60 m / s)
-Processing speed: 230 kg / hr.

Each component used for production of the surfactant-containing particles is as follows.
Fatty acid methyl ester sulfonate-containing paste (fatty acid chain length: carbon number 16/18 (content ratio 8/2), active ingredient 63% by mass, the following nonionic surfactant 16% by mass, di-salt and methyl sulfate, etc. Impurities 8 mass%, moisture 13 mass%).
-Fluorescent agent: Chino Pearl CBS-X (manufactured by Ciba Japan Co., Ltd.).
Linear alkyl benzene sulfonic acid (LAS-H): AV value (mg potassium hydroxide required to neutralize 1 g of LAS-H) = 180.0, Raipon LH-200 (manufactured by Lion Corporation). In Table 1, LAS-H is described as linear alkylbenzene sulfonate potassium (LAS-K) neutralized with a 48% by mass potassium hydroxide solution in a slurry for spray drying.
-Salt of acrylic acid-maleic acid copolymer: Aqualic TL-400 (pure 40% by mass aqueous solution, manufactured by Nippon Shokubai Co., Ltd.).
Nonionic surfactant: ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms, manufactured by Ecogreen Oleochemicals) with an average of 15 mol of ethylene oxide added (manufactured by Lion Corporation).
A-type zeolite: Thai silicate (pure content 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.).
Sodium carbonate: granular ash (manufactured by Soda Ash Japan Co., Ltd.).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.).
Sodium sulfate: neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Kasei Co., Ltd.).
Potassium hydroxide: caustic potash (48% by mass) (manufactured by Asahi Glass Co., Ltd.)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content 67% by mass, titer: 40 to 45 ° C., fatty acid composition: C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 mass%, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight: 289).

(Examples 1-8, Comparative Example 2)
In accordance with the composition shown in Table 2, a detergent addition particle was produced by the following procedure using a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) having a shovel-shaped shovel and a clearance between the shovel and the wall surface of 5 mm. . The components (A) and (B) were charged into the mixing apparatus at a filling rate of 30% (based on the component (A)) and stirred at a main shaft of 200 rpm for 2 minutes (the chopper was stopped). While stirring the component (A) and the component (B), the component (C) (60 ° C.) was added over 30 seconds, and the mixture was further stirred for 2 minutes and 30 seconds to obtain particles for adding detergents in each example. . When the obtained particles for adding a cleaning agent were observed with a microscope, the component (B) was attached to the surface of the component (A).
In accordance with the particle mixing ratio in Table 2 (mass ratio represented by surfactant-containing particles / detergent-added particles), the detergent-added particles and the surfactant-containing particles are powder-mixed to obtain a granular detergent. . About the obtained granular washing | cleaning agent, a solubility and a solidification inhibitory effect are evaluated and the result is shown in a table | surface.

Example 9
After adding the component (C), particles for detergent addition were obtained in the same manner as in Example 1 except that the A-type zeolite was added. When the obtained particles for adding a cleaning agent were observed with a microscope, the component (B) was attached to the surface of the component (A).
In accordance with the particle mixing ratio in Table 2, the detergent addition particles and the surfactant-containing particles were powder-mixed to obtain a granular detergent. About the obtained granular washing | cleaning agent, a solubility and a solidification inhibitory effect are evaluated and the result is shown in a table | surface.

(Comparative Example 1)
According to the composition of the detergent additive particles in Table 2, the component (A) and the component (B) were powder-mixed to obtain detergent additive particles. In the detergent addition particles, the component (A) and the component (B) are present as independent particles.
In accordance with the particle mixing ratio in Table 2, the detergent addition particles and the surfactant-containing particles were powder-mixed to obtain a granular detergent. About the obtained granular washing | cleaning agent, a solubility and a solidification inhibitory effect are evaluated and the result is shown in a table | surface.

(Comparative Example 3)
A granular detergent was obtained in the same manner as in Comparative Example 1 except that the component (A) was changed to particles for detergent addition. About the obtained granular washing | cleaning agent, a solubility and a solidification inhibitory effect are evaluated and the result is shown in a table | surface.

(Evaluation method)
<Solidification suppression effect>
Using paper consisting of three layers of coated cardboard (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, A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was prepared, and 1.1 kg of the granular cleaning agent of each example was placed in the box. The box containing the granular detergent was sealed and dropped 10 times from a height of 10 cm to increase the contact point between the particles. Thereafter, the box containing the granular detergent was stored in a constant temperature and humidity chamber for 14 days. The constant temperature and humidity chamber was repeatedly operated at 45 ° C. and 85% RH for 8 hours and at 25 ° C. and 65% RH for 16 hours. After storage for 14 days, the box containing the granular cleaning agent was taken out from the constant temperature and humidity chamber, and left for 6 hours at a temperature of 20 ° C. and 60% RH (storage processing).
After the storage treatment, the granular detergent in the box was gently transferred onto a sieve having an opening of 5 mm. After gently shaking the sieve 10 times horizontally, the residue on the sieve was weighed. The mass (residual amount) of the residue on the sieve was classified into the following evaluation criteria, and the solidification suppression effect was evaluated. If the remaining amount is less than 30 g, it can be said that there is no practical problem.

≪Evaluation criteria≫
A: The remaining amount is less than 15 g.
○: The remaining amount is 15 g or more and less than 30 g.
Δ: The remaining amount is 30 g or more and less than 60 g.
X: The remaining amount is 60 g or more.

<Solubility>
Put 30L of tap water at 5 ° C into a two-tank washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric Corporation), and put 6 cotton shirts, 2 polyester shirts, and 2 acrylic shirts as washing items. The bath ratio (the mass of water relative to the mass of the object to be washed) was adjusted to 20 times. Each item to be washed was folded and floated on the surface of the water. 30 g of the granular cleaning agent of each example was placed on the center of the object to be cleaned, immersed for 4 minutes with the object to be cleaned, and then stirred for 3 minutes with a weak water flow. After draining, the objects to be washed were dehydrated for 1 minute.
Next, the object to be washed and the inside of the washing machine were visually observed, and the solubility was evaluated according to the following evaluation criteria. Considering usability at home, the evaluations “◎” and “」 ”were judged to be acceptable.

≪Evaluation criteria≫
(Double-circle): The undissolved residue of a granular cleaning agent is not recognized.
○: Slightly undissolved residue of granular detergent is observed.
(Triangle | delta): The undissolved residue of a granular cleaning agent is conspicuous.
X: The undissolved residue of the granular cleaning agent is remarkable.

As shown in Table 2, in Examples 1 to 9 to which the present invention was applied, the solidification suppressing effect was “◯” to “◎”, and the solubility was “◯” to “◎”. Especially, Example 1 whose B / A particle diameter ratio is 0.13 was excellent in the solidification suppression effect compared with Examples 2 and 5 whose B / A particle diameter ratio is less than 0.1. Moreover, Example 1 was excellent in the solidification inhibitory effect and solubility compared with Example 3 whose B / A particle diameter ratio is more than 0.2.
Comparative Example 1 in which the (A) component and the (B) component were used without granulation, Comparative Example 2 in which the B / A particle size ratio was 0.5, and Comparative Example 3 in which only the (A) component was used The solubility was “×” or “Δ”.
From the above results, it was found that the solubility and the solidification suppressing effect of the granular cleaning agent can be further improved by applying the present invention.

Claims (3)

(A) component: granulated product of alkali metal sulfate particles, (B) component: alkali metal hydrogen carbonate particles, and (C) component: binder.
The ratio represented by [Average particle diameter of the particle group of the component (B) to be blended] / [Average particle diameter of the particle group of the component (A) to be blended] is 0.3 or less. Particles for adding detergent.   The particle for detergent addition according to claim 1, wherein the component (B) is attached to the surface of the component (A).   A granular cleaning agent comprising the cleaning agent addition particles according to claim 1 or 2.