KR20140118730A - Granular detergent composition - Google Patents

Abstract

Provided is a granular detergent composition having good solubility in water and good flowability of a particle group. For this, a granular detergent composition is obtained by dry mixing a particle group (A) including a surfactant, a particle group (B) composed of an aqueous inorganic salt, and a particle group (C) composed of an aqueous saturated aliphatic acid salt, and satisfies the following Formulae (1) to (5). 0.45 < r/R < 1.00 ··· (1), (a×R^3)/(b×r^)×0.3 < X/Y < (a×R^3/(b×r^3)×3.0 ··· (2), 70 <= X+Y < 100 ··· (3), 0.40 < n/m < 1.10 ··· (4), s <= r/5 ··· (5)) [R: mean particle diameter of particle group (A), r: mean particle diameter of particle group (B). a: volume density of particle group (A). b: volume density of particle group (B). X: amount of particle group (A). Y: amount of particle group (B). m: half width of particle size distribution of particle group (A). n: half width of particle size distribution of particle group (B). s: mean particle diameter of particle group (C).].

Description

GRANULAR DETERGENT COMPOSITION [0001]

The present invention relates to a granular detergent composition.

BACKGROUND ART Conventionally, granular detergents have been generally used as detergents used in washing of medical products (clothes), but in recent years, migration from granular detergent to liquid detergents has been progressing at home. One of the factors is that the consumer has an image that "the granular detergent is difficult to melt and remains soluble". Various techniques for improving the solubility of the granular detergent in water have been studied (for example, Patent Documents 1 to 5). It is considered effective to reduce the particle diameter of the particles constituting the granular detergent in order to improve the image &quot; granular detergent is hard to melt and remains soluble &quot;. As the particle size becomes smaller, not only the dissolution time of individual particles is shortened, but also it is easy to melt even in appearance.

Patent Document 1: Japanese Patent Application Publication No. 7-509267 Patent Document 2: Japanese Patent Application Laid-Open No. 11-172292 Patent Document 3: Japanese Patent No. 3249815 Patent Document 4: Japanese Patent No. 3516636 Patent Document 5: Japanese Patent Application Laid-Open No. 2002-266000

However, when the average particle diameter of the particles containing the surfactant is less than 300 탆, the solubility is lowered. Since the surface of the particles containing the surfactant tends to become sticky and the particle size becomes smaller, the contact point of the particles increases even if the solubility of one lip (particle) increases, so that the particle group Aggregation tends to occur at the time of contact. This aggregation is particularly likely to occur when the mechanical force applied to the particle groups is low, such as when the particles are sandwiched by a cloth with a low bath ratio. When aggregation of the particle groups occurs, the solubility as a whole is lowered. In addition, there is a concern that the fluidity is lowered and the usability is deteriorated.

Therefore, even when the average particle size is reduced, the granular detergent is required which is not easily aggregated even when the mechanical force is low in the particle group, exhibits excellent solubility in water, and has good fluidity.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a granular detergent composition which is excellent in solubility in water and which is excellent in fluidity of a particle group.

The present invention relates to a water-in-oil emulsion composition comprising a particle group (A) containing a surfactant, a particle group (B) comprising a water-soluble inorganic salt, and a particle group (C)

And satisfies the following formulas (1) to (5).

0.45 &lt; r / R &lt; 1.00 ... (One)

(a × R ³ ) / (b × r ³ ) × 0.3 <X / Y <(a × R ³ ) / (b × r ³ ) (2)

70? X + Y &lt; 100 ... (3)

0.40 &lt; n / m &lt; 1.10 ... (4)

s? r / 5 ... (5)

Note that the symbols in the expressions (1) to (5) have the following meanings.

R: Average particle size (탆) of the above-mentioned particle group (A).

r: average particle diameter (占 퐉) of the particle group (B).

a: bulk density (g / cm3) of the above-mentioned particle group (A).

b: bulk density (g / cm &lt; 3 &gt;) of the particle group (B)

X: Content (mass%) of the above-mentioned particle group (A).

Y: content (mass%) of the above-mentioned particle group (B).

m is a half value width (占 퐉) of the particle size distribution of the particle group (A).

n is the half width (占 퐉) of the particle size distribution of the particle group (B).

s: average particle diameter (占 퐉) of the particle group (C).

According to the present invention, it is possible to provide a granular detergent composition which is excellent in solubility in water and is excellent in fluidity of the particle group.

1 is a schematic view for explaining the equation (1).
Fig. 2 is a graph of particle size distribution for explaining equation (4). Fig.
Fig. 3 is a graph of particle size distribution for explaining equation (4). Fig.

The granular detergent composition of the present invention comprises a particle group (A) containing a surfactant, a particle group (B) composed of a water-soluble inorganic salt, and a particle group (C)

Satisfy the following formulas (1) to (5).

0.45 &lt; r / R &lt; 1.00 ... (One)

(a × R ³ ) / (b × r ³ ) × 0.3 <X / Y <(a × R ³ ) / (b × r ³ ) (2)

70? X + Y &lt; 100 ... (3)

0.40 &lt; n / m &lt; 1.10 ... (4)

s? r / 5 ... (5)

Note that the symbols in the expressions (1) to (5) have the following meanings.

R: Average particle size (탆) of the above-mentioned particle group (A).

r: average particle diameter (占 퐉) of the particle group (B).

a: bulk density (g / cm3) of the above-mentioned particle group (A).

b: bulk density (g / cm &lt; 3 &gt;) of the particle group (B)

X: Content (mass%) of the above-mentioned particle group (A).

Y: content (mass%) of the above-mentioned particle group (B).

m is the half width (占 퐉) of the particle size distribution of the particle group (A).

n is the half width (占 퐉) of the particle size distribution of the particle group (B).

s: average particle diameter (占 퐉) of the particle group (C).

Here, in the present invention, the average particle diameter is calculated by dividing the average diameter (the arithmetic average particle diameter in the volume% mode) (D (D)) of the volume weight (volume weight) in the particle size distribution (volume frequency distribution) measured by the laser diffraction / scattering method ) = Σn _i x _i ⁴ / Σn _i x _i ³ (x _i = the center value of the channel, n _i = the percentage of particles in the i th channel). The particle size distribution (particle size distribution) can be measured using a known laser diffraction scattering particle size distribution measuring apparatus (for example, LS 13 320 manufactured by Beckman Coulter).

Bulk density is a value measured according to JIS K3362 (2008).

The half width of the particle size distribution represents the peak width at a position half the height of the peak top of the particle size distribution (transverse axis: particle diameter (占 퐉) and longitudinal axis (frequency (%)) measured as described above.

The particle groups (A) to (C) will be described later in detail.

In the present invention, a balance of the particle diameter ratio and the number of particles of the particle group (A) and the particle group (B) and the blending of the particle group (C) of a specific particle diameter become important. By combining the particle group (A) and the particle group (B) so as to satisfy the formulas (1) to (4), the solubility of the granular detergent composition in water is improved. Further, by further blending the particle group (C) satisfying the formula (5), the solubility in water is further improved, and further, the flowability of the granular detergent composition is also improved.

The formula (1) is preferably 0.45 <r / R <1.00 and 0.55 <r / R <0.90.

The formula (1) shows the relationship between the average particle size R of the particle group A and the average particle size r of the particle group B.

When r / R exceeds 0.45, the granular detergent composition shows good solubility in water even in a low-temperature bath. In addition, the granular detergent composition has good fluidity.

This is because the contact between the particles of the particle group A (hereinafter, also referred to as A particles) is reduced by the function of the particles of the particle group B (hereinafter also referred to as B particles) as spacers, The aggregation at the time of dissolution is suppressed. It is considered that the decrease of the fluidity due to adhesion of the A particles to each other is also suppressed because the contact points of the A particles are reduced.

1, when the particle group A is arranged such that four A particles are in contact with each other in two in the longitudinal direction and two in the transverse direction, . B particles having a diameter r (the distance between the centers of the two opposed two A particles - R / 2 x 2) or less may enter the gap. At this time, r / R becomes about 0.41.

When r / R exceeds 0.45, as shown in Fig. 1 (b), B particles become spacers, and the contact points of the A particles decrease.

When the ratio r / R is 0.41 or less, as shown in Fig. 1 (a), the B particle enters the gap between the A particles, and thus the contact point between the plurality of A particles is the same as the case where there is no B particle. When r / R is more than 0.41 but not more than 0.45, the contact between the A particles hardly decreases even when B particles enter.

When r / R is 1.00 or more, B particles function as spacers, but since the mass per one B particle increases, the number of B particles relatively decreases and there is a possibility that the contact points of the A particles can not be sufficiently reduced have.

The formula (2) is (a × R ³ ) / (b × r ³ ) × 0.3 <X / Y <(a × R ³ ) / (b × r ³ ) × 3.0.

If X / Y is more than 0.3 times to 3.0 times (a × R ³ ) / (b × r ³ ), the balance between the number of A particles and the number of B particles in the granular detergent composition is good, The solubility of the polymer is improved.

The formula (2) can be said to indicate the relationship between the number of A particles and the number of B particles in the granular detergent composition.

That is, the mass per A particle is found by a × 4 / 3π × (R / 2 × 10 ^-4 ) ³ . Therefore, when the number of A particles in the granular detergent composition is p, X can be expressed as {a 占 4/3? 占 (R / 2 占^10-4 ) ³占 p. Similarly, when the number of B particles in the granular detergent composition is q, the mass per particle B is obtained as b × 4 / 3π × (r / 2 × 10 ^-4 ) ³ , b × 4 / 3π × (R / 2 × 10 ^-4 ) ³ } × q.

Therefore, X / Y is, [{a × 4 / 3π × (R / 2 × 10 -4) 3} × p] / {{b × 4 / 3π × (R / 2 × 10 -4) 3} × q } And (a × R ³ ) / (b × r ³ ) × (p / q) if these expressions are summarized. When this is modified by substituting X / Y in the formula (2), 0.3 <p / q <3.0, and the relationship between p and q is obtained.

As described above, the B particles are considered to function as a spacer between the particles of the particle group (A), and the B particles are included as the number of particles satisfying 0.3 < p / q < 3.0, .

The formula (3) is preferably 70? X + Y &lt; 100, 80? X + Y <100 and 90? X + Y <100.

When X + Y (the total content of the particle group (A) and the particle group (B) with respect to the total mass of the granular detergent composition) is 70 mass% or more, the granular detergent composition has good solubility in water, Is also good. On the other hand, when the value of X + Y is 100, that is, when the particle group (C) is not included, the flowability of the granular detergent composition may be lowered.

The formula (4) is preferably 0.40 <n / m <1.10 and 0.60 <n / m <1.10.

Formula (4) shows the relationship between the spread of the particle size distribution of the particle group (A) and the spread of the particle size distribution of the particle group (B).

Figs. 2 to 3 show a specific example. Fig. 2 is an example of a graph in which the particle size distribution of one kind of particle group (A) is overlapped with the particle size distribution of two kinds of particle groups (B) having the same average particle size and different n. 3 is a graph showing the particle size distribution of the particle group A in which the average particle size is the same but the particle size is narrower than that of the particle group A in Fig.

As shown in these drawings, when the full width at half maximum (m, n) is widened, the ratio of particles whose particle diameters deviate from the average particle diameters increases and the misalignment also increases. If n / m is 1.10 or more (when the particle size distribution of the particle group (B) is larger than the particle size distribution of the particle group (A)), or if the particle group (A) Is narrower than the particle size distribution of the particle group (B)), at the individual particle level, the proportion of the B particles which do not satisfy the formula (1) and become the spacer increases. On the other hand, when n / m is less than 0.40 (the particle size distribution of the particle group B is narrower than the particle size distribution of the particle group A, or the particle size distribution of the particle group A is smaller than the particle size distribution of the particle group B) , The ratio of A particles in which B particles do not become a spacer increases.

By satisfying the formula (4), it is considered that the B particles to be the spacer exist in a sufficient number with respect to the A particles, and the contact between the A particles can be sufficiently reduced, and the effect such as improvement in the solubility is sufficiently obtained.

The formula (5) is preferably s? R / 5 and s? R / 10.

The particle group (C) is composed of a water-soluble saturated fatty acid salt. By including the particle group (C) satisfying the formula (5), the solubility in water is further improved, and further the fluidity of the granular detergent composition is improved.

The reason for achieving the above effect is that the water-soluble saturated fatty acid salt has an average particle diameter (s) of 1/5 or less of the average particle diameter (r) of the particle group (B) Hereinafter also referred to as C particle) functions as a lubricant. That is, the C particles are good in mixing with the A particles and the B particles, and are adhered to the surfaces of the A particles or the B particles at the time of powder mixing or are distributed in the vicinity of their surfaces. It is believed that the C particles make it easy for the B particles to slip into the gap between the A particles, sufficiently function as the spacer for the B particles, and improve the solubility in water. Further, it is considered that the deterioration of the fluidity due to adhesion or friction of the A particle B particles is suppressed.

In order to sufficiently obtain the above effect, the water-soluble saturated fatty acid salt is mixed with the particle groups (A) and (B) (powder mixture) in the particle state (as the particle group (C)) instead of coating by spraying or the like.

&Lt; Particle group (A) >

The particle group (A) is a group of particles containing a surfactant.

[Surfactants]

The surfactant is not particularly limited, and a surfactant mixed with a granular detergent or the like can be used, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

The anionic surfactant is not particularly limited as long as it is used in granular detergent, and examples thereof include the following.

(1-1)? -Sulfo fatty acid alkyl ester salt.

The kind of the? -sulfo fatty acid alkyl ester salt is not particularly limited, and any? -sulfo fatty acid alkyl ester salt used in a general granular detergent composition can be suitably used and is preferably represented by the following formula (11).

R ^{11 is} -CH (SO ₃ M) -COOR ¹² (11)

In the formula (11), R ¹¹ is a linear or branched alkyl group having a carbon number of 8 to 20, preferably a carbon number of 14 to 16, or a linear or branched alkenyl group having a carbon number of 8 to 20.

R ¹² is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group and an isopropyl group, and more preferably a methyl group, an ethyl group or a propyl group, and a methyl group is particularly preferable.

M represents an ion, for example, an alkali metal salt such as sodium or potassium; Amine salts such as monoethanolamine, diethanolamine and triethanolamine; Ammonium salts and the like. Among them, an alkali metal salt is preferable.

As the? -sulfo fatty acid alkyl ester salt, for example,? -sulfo fatty acid methyl ester sodium salt (MES) is preferable.

(1-2) A straight-chain or branched-chain alkylbenzenesulfonic acid salt (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.

(1-3) alkanesulfonic acid salt having 10 to 20 carbon atoms.

(1-4)? -Olefin sulfonic acid salt (AOS) having 10 to 20 carbon atoms.

(1-5) an alkylsulfate or alkenylsulfate (AS) having 10 to 20 carbon atoms;

(1-6) 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) (Or alkenyl) ether sulfates (AES) having from 1 to 20 straight-chain or branched alkyl (or alkenyl) groups.

(1-7) 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) (Or alkenyl) phenyl ether sulfates having from 1 to 20 straight or branched chain alkyl (or alkenyl) groups.

(1-8) an alkylene oxide having 2 to 4 carbon atoms, or an ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) ether carboxylate having a straight or branched chain alkyl (or alkenyl) group of 1 to 20 carbon atoms.

(1-9) An alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.

(1-10) monoalkyl, dialkyl or sesquioalkyl phosphates having an alkyl group having 10 to 20 carbon atoms.

(1-11) polyoxyethylene monoalkyl, dialkyl or sesquioalkyl phosphates.

(1-12) High fatty acid salts having 10 to 20 carbon atoms (soaps).

These anionic surfactants can be used as alkali metal salts such as sodium salt and potassium salt, amine salts, ammonium salts and the like. These anionic surfactants may be used singly or in combination of two or more.

The nonionic surfactant is not particularly limited as far as it is conventionally used for granular detergent, and examples thereof include the following.

(2-1) an aliphatic alcohol having 6 to 22, preferably 8 to 18 carbon atoms, an alkylene oxide having 2 to 4 carbon atoms on an average of 3 to 30 mol, preferably 3 to 20 mol, more preferably 5 to 20 mol Polyoxyalkylene alkyl (or alkenyl) ether. Of these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. Examples of the aliphatic alcohol used herein include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

(2-2) polyoxyethylene alkyl (or alkenyl) phenyl ether.

(2-3) Fatty acid alkyl ester alkoxylate to which alkylene oxide is added between ester bonds of long chain fatty acid alkyl ester.

(2-4) Polyoxyethylene sorbitan fatty acid ester.

(2-5) Polyoxyethylene sorbit fatty acid esters.

(2-6) Polyoxyethylene fatty acid ester.

(2-7) Polyoxyethylene hydrogenated castor oil.

(2-8) Glycerol fatty acid esters.

Examples of the fatty acid alkyl ester alkoxylates of (2-3) 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 of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (an oxyalkylene group), and ethylene oxide, propylene oxide and the like are preferable. q represents an average addition mole number of the alkylene oxide and is generally 3 to 30, preferably 5 to 20. R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent. ]

These nonionic surfactants may be used singly or in combination of two or more.

Among the nonionic surfactants described above, the nonionic surfactant of the above (2-1) is preferable, and in particular, a poly (alkylene oxide) having 2 to 4 carbon atoms in an amount of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 12 to 16 carbon atoms. Oxyalkylene alkyl (or alkenyl) ethers are preferred.

Further, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having an HLB of 9 to 16 and a melting point of 50 DEG C or less, fatty acid to which ethylene oxide is added to fatty acid methyl ester Methyl ester ethoxylate, fatty acid methyl ester ethoxypropoxylate and the like in which ethylene oxide and propylene oxide are added to fatty acid methyl ester are suitably used. The HLB of the nonionic surfactant in the present specification is a value obtained by the Griffin method (Yoshida, Shindou, Ogaki, Yamanaka Co-ed., &Quot; New Edition Surfactant Handbook & , Page 234).

The melting point in the present specification is a value measured by the melting point measurement method described in JIS K0064-1992, Method of measuring melting point and melting range of a chemical product.

Examples of the cationic surfactant include the following.

(3-1) Di long chain alkyl di short chain alkyl type quaternary ammonium salt.

(3-2) Mono long-chain alkyltri- short chain alkyl type quaternary ammonium salt.

(3-3) Tree long-chain alkyl mono-short chain alkyl-type quaternary ammonium salt.

However, the above &quot; long chain alkyl &quot; represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. The "short-chain alkyl" includes substituents such as a phenyl group, a benzyl group, a hydroxyl group, and a hydroxyalkyl group, and may have an ether bond between carbon atoms. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; Benzyl group; A hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; A polyoxyalkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms is suitable.

Examples of the amphoteric surfactant include imidazoline amphoteric surfactants and amide betaine amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauric acid amide propyl betaine may be mentioned as suitable.

These surfactants may be used alone or in combination of two or more.

The particle group (A) preferably contains an anionic surfactant as a surfactant, and among them, at least one kind selected from an? -Sulfo fatty acid alkyl ester salt and an LAS salt .

It is also preferable that the particle group (A) contains a nonionic surfactant as a surfactant. As the nonionic surfactant, for example, the nonionic surfactant (polyoxyalkylene alkyl (or alkenyl) ether) of the above (2-1) is preferable.

When an anionic surfactant and a nonionic surfactant are used in combination, their mass ratio (anionic surfactant / nonionic surfactant) in the particle group (A) is preferably from 1 to 10 More preferably from 2 to 6, and even more preferably from 3 to 5.

The content of the surfactant in the particle group (A) is not particularly limited, but is preferably 10 to 30% by mass, more preferably 15 to 30% by mass with respect to the total mass of the particle group (A) By mass to 30% by mass.

[Water-soluble inorganic salt]

The particle group (A) preferably contains a water-soluble inorganic salt in addition to the surfactant, from the viewpoint of the fluidity and manufacturability of the particles.

As the water-soluble inorganic salt, a water-soluble inorganic salt generally used as a granular detergent or the like as a cleansing builder and the like can be used, and for example, an alkali metal carbonate such as sodium carbonate and potassium carbonate; Alkali metal hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquiathanate; Alkali metal sulfites such as sodium sulfite and potassium sulfite; (For example, a crystalline alkali metal silicate such as "Na-SKS-6" (δ-Na ₂ O 揃 2SiO ₂ ) manufactured by Clariant Japan Co., Ltd.), amorphous alkali metal silicate; Sulfates such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; Phosphates such as pyrophosphate, tripolyphosphate, orthophosphate, metaphosphate, hexametaphosphate, and phytic acid; And a complex of sodium carbonate and an amorphous alkali metal silicate (for example, NABION 15 (trade name) manufactured by Rhodia). These water-soluble inorganic salts may be used singly or in combination of two or more kinds.

Among the above-mentioned water-soluble inorganic salts to be contained in the particle group (A), alkali metal carbonate and sulfate are preferable, and sodium carbonate, potassium carbonate and sodium sulfate are more preferable. These may be used singly or in combination of two or more.

Of these, sodium carbonate and sodium sulfate are preferably used in combination. The use of sodium carbonate and sodium sulfate tends to increase the strength and fluidity of the particle group (A).

When sodium carbonate and sodium sulfate are used in combination, the mass ratio represented by sodium carbonate / sodium sulfate in the particle group (A) is preferably 1 to 10, more preferably 1.5 to 10. When the mass ratio of sodium carbonate / sodium sulfate is 1 or more, the washing power of the particle group (A) tends to be further improved. When the mass ratio is 10 or less, the particle group (A) has better strength and fluidity.

As sodium carbonate and sodium sulfate, anhydrides are suitably used. In the present specification, the description of "sodium carbonate" and "sodium sulfate" indicates an anhydride.

The content of the water-soluble inorganic salt in the particle group (A) is not particularly limited, but is preferably within a range of 1 to 5 in mass ratio (water-soluble inorganic salt / surfactant) to the surfactant in the particle group (A) Do. The water-soluble inorganic salt / surfactant is more preferably 2 to 4, and still more preferably 2 to 3. When the water-soluble inorganic salt / surfactant is within the above-mentioned range, the granular detergent composition prepared using the particle group (A) is excellent in solubility in water, and the fluidity at the initial stage and the aging tends to be good. When the amount of the water-soluble inorganic salt / surfactant is 1 or more, excellent detergency can be obtained while suppressing the concentration of the surfactant to a low level. If the amount of the water-soluble inorganic salt / surfactant is 5 or less, the production (assembly) of the particle group (A) can be performed without any problem.

[Other optional ingredients]

The particle group (A) may also contain other components than the surfactant and the water-soluble inorganic salt, if necessary. As the other components, known components incorporated in the granular detergent composition can be used. For example, organic builders, water-insoluble inorganic salts, fluorescent whitening agents, polymers, enzyme stabilizers, anti-caking agents, reducing agents, , a pH adjusting agent, and the like.

Examples of the organic builder include aminocarboxylic acid salts such as nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt,? -Alanine diacetate salt, aspartic acid diacetate salt, methylglycine diacetate salt and iminodiacetic acid salt; Hydroxyaminocarboxylic acid salts such as serindiacetic acid salt, hydroxyiminodiacetic acid salt, hydroxyethylethylenediamine triacetate and dihydroxyethyl glycine salt; Hydroxycarboxylic acid salts such as hydroxyacetic acid salts, tartaric acid salts, citric acid salts and gluconic acid salts; Cyclocarboxylic acid salts such as pyromellitic acid salts, benzopolycarboxylic acid salts and cyclopentanetetracarboxylic acid salts; Ether carboxylate such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate; Salts of polyacetal carboxylic acids such as polyacrylic acid salts, salts of acrylic acid-allyl alcohol copolymer, salts of acrylic acid-maleic acid copolymer and polyglyoxylic acid; Salts of acrylic acid polymers or copolymers, such as hydroxy acrylic acid polymers, polysaccharides-acrylic acid copolymers; Salts of polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, and aspartic acid; Polysaccharide oxides such as starch, cellulose, amylose and pectin, polysaccharide derivatives such as carboxymethyl cellulose, and the like.

Among these, the detergency and the contamination dispersibility in the washing liquid are further improved. Therefore, it is preferable to use a salt of a citrate, an aminocarboxylate, a hydroxyaminocarboxylate, a polyacrylate, a salt of an acrylic acid- It is preferred to use a salt.

The content of the organic builder in the particle group (A) is not particularly limited, but is preferably from 1 to 20 mass%, more preferably from 1 to 10 mass%, and even more preferably from 2 to 5 mass%, based on the total mass of the particle group (A) % By mass is more preferable.

Examples of the water-insoluble inorganic salt include zeolite, clay mineral, and the like.

Among them, zeolite is suitably used as a builder contributing to improvement of cleaning power. Zeolite is a generic name of aluminosilicate, and as the aluminosilicate, either crystalline or amorphous (amorphous) can be used. Crystalline aluminosilicates are preferred in terms of cation exchange capacity. As the crystalline aluminosilicate, A type, X type, Y type, P type zeolite and the like are suitable.

The content of the zeolite in the particle group (A) is not particularly limited, but is preferably 1 to 15 mass%, more preferably 3 to 15 mass%, and more preferably 5 to 10 mass%, based on the total mass of the particle group (A) % Is more preferable. If the lower limit of the above range is exceeded, the effect of improving the detergency by using the zeolite is easily obtained, and if it is less than the upper limit value, the deterioration of the rinsing property by the use of the zeolite is hardly caused.

However, from the viewpoint of the apparent solubility of the granular detergent composition, the content of the zeolite in the granular group (A) is preferably 10% by mass or less, more preferably 10% by mass or less with respect to the total mass of the granular detergent composition, Of the total amount of the particles.

[Average particle size]

The average particle diameter (R) of the particle group (A) can be suitably set within a range satisfying the formula (1) and is not particularly limited, but is usually in the range of 100 to 500 mu m, preferably 100 to 300 mu m , More preferably 100 to 250 占 퐉, and particularly preferably 100 to 200 占 퐉.

When the average particle diameter of the particle group (A) is in the above range, the time required for dissolving the A particles is short and the solubility is good. Further, when the average particle diameter R is reduced, the average particle size of the particle groups B and C is relatively small, and the average particle size of the whole granular detergent composition is small. Therefore, the dissolution time of the granular detergent composition as a whole is shortened, and it is possible to give an image that it is easy for the user to dissolve.

On the other hand, when the average particle diameter of the particle group (A) is less than 100 m, the average particle diameter of the particle groups (B) and (C) becomes very small in order to satisfy the formulas (1) and (5) do. In addition, even when the particle group (C) is blended, coalescence tends to occur, and there is a possibility that both the solubility and the fluidity are lowered.

[Half width of particle size distribution]

The half width (m) of the particle size distribution of the particle group (A) can be appropriately set within a range satisfying the formula (4).

[Bulk density]

The bulk density (a) of the particle group (A) is not particularly limited, but is preferably 0.6 to 1.2 g / cm 3, more preferably 0.8 to 1.0 g / cm 3.

[Water content (moisture content)]

The water content of the particle group (A) is not particularly limited, but is preferably from 4 to 10 mass%, more preferably from 5 to 9 mass%, and still more preferably from 5.5 to 8.5 mass%. When the water content is 4 mass% or more, the solubility in water is good, and when it is 10 mass% or less, the fluidity after storage is good.

The water content is a value measured as an evaporation volatile content after heating at 130 占 폚 for 20 minutes by an infrared moisture meter (for example, Kett moisture meter, Kato Scientific Inc.).

[Compounding amount]

The blending amount X of the particle group (A) in the granular detergent composition can be suitably set within a range satisfying the formulas (2) and (3), and is not particularly limited. By mass or more, more preferably 60% by mass or more. When the amount is 50% by mass or more, good cleaning power can be obtained. The upper limit of the blending amount (X) is preferably 90% by mass or less, more preferably 85% by mass or less, in view of balance with other components.

&Lt; Particle group (B) >

The particle group (B) is a particle composed of a water-soluble inorganic salt.

As the water-soluble inorganic salt, a water-soluble inorganic salt generally used as a granular detergent or the like as a cleansing builder and the like can be used, and for example, an alkali metal carbonate such as sodium carbonate and potassium carbonate; Alkali metal sulfites such as sodium sulfite and potassium sulfite; Alkali metal hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquiathanate; (For example, a crystalline alkali metal silicate such as "Na-SKS-6" (δ-Na ₂ O 揃 2SiO ₂ ) manufactured by Clariant Japan Co., Ltd.), amorphous alkali metal silicate; Sulfates such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; Phosphates such as pyrophosphate, tripolyphosphate, orthophosphate, metaphosphate, hexametaphosphate, and phytic acid; And a complex of sodium carbonate and an amorphous alkali metal silicate (for example, NABION 15 (trade name) manufactured by Rhodia).

Among the above-mentioned water-soluble inorganic salts constituting the particle group (B), alkali metal hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquicarbonate are preferable from the viewpoint of solubility and washing power, and sodium hydrogencarbonate is particularly preferable Do.

One or more B particles constituting the particle group (B) may be used. When two or more kinds of B particles are used in combination, it is preferable to use those having the same particle size distribution as each B particle.

[Average particle size]

The average particle diameter r of the particle group B can be suitably set in consideration of the average particle diameter R of the particle group A within a range satisfying the formula (1) and is not particularly limited, Mu] m, more preferably 55 to 240 mu m, and particularly preferably 100 to 200 mu m.

[Half width of particle size distribution]

The half width (n) of the particle size distribution of the particle group (B) can be appropriately set within the range satisfying the formula (4).

[Bulk density]

The bulk density (b) of the particle group (B) is not particularly limited, but is preferably 0.6 to 1.7 g / cm3, more preferably 0.8 to 1.5 g / cm3.

[Compounding amount]

The compounding amount (Y) of the particle group (B) in the granular detergent composition can be suitably set within a range satisfying the formulas (2) and (3), and is not particularly limited. By mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. When the amount is 10% by mass or more, the granular detergent composition has good solubility in water. The upper limit of the compounding amount (Y) is preferably 30% by mass or less in consideration of the balance with other components.

&Lt; Particle group (C) >

The particle group (C) is a particle composed of a water-soluble saturated fatty acid salt.

Examples of the water-soluble saturated fatty acid salt include a salt of a straight chain or branched chain saturated fatty acid having 12 to 16 carbon atoms. Examples of the salt include alkali metal salts such as sodium and potassium, and calcium salts.

As the water-soluble saturated fatty acid salt constituting the particle group (C), sodium palmitate and sodium myristate are preferable.

One or more C particles constituting the particle group (C) may be used.

[Average particle size]

The average particle diameter (s) of the particle group (C) can be suitably set in consideration of the average particle diameter (r) of the particle group (B) within a range satisfying the formula (5) More preferably 5 to 50 占 퐉. When the thickness is 60 μm or less, the solubility of the C particles is also good. Further, the smaller the average particle diameter s is, the more easily the desired effect can be obtained with the small particle group C. When the average particle diameter s is 5 占 퐉 or more, handling (fluidity of the particle group) is also good.

[Compounding amount]

The blending amount of the particle group (C) in the granular detergent composition is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and more preferably 0.2 to 1% by mass relative to the total mass of the granular detergent composition desirable. Within this range, the solubility is not deteriorated and the fluidity is good.

<Optional ingredients>

The granular detergent composition of the present invention may contain a bleaching agent, a bleaching activator, a bleach activating catalyst, an enzyme, a re-pollution preventing agent (such as carboxymethyl cellulose), a defoaming agent, a surface coating agent (Zeolite and the like), an antioxidant, a pigment, and the like.

These optional components may be mixed with the particle groups (A) to (C) as a group of particles or may be attached to at least one of the particle groups (A) to (C) by spraying or the like.

&Lt; Process for producing granular detergent composition >

The granular detergent composition of the present invention can be produced by powder mixing such that the particle group (A), the particle group (B) and the particle group (C) satisfy the above formulas (1) to .

In the granular detergent composition obtained by powder mixing these particle groups, particles (A particles, B particles, C particles) of each particle group exist as independent particles.

Each of the particle groups (A) to (C) may be either a commercially available product or a product prepared by a known production method. For example, the particle group (A) can be produced by a production method described later. When a commercial product is used, it may be adjusted to a desired average particle size and particle size distribution by performing a sieve or the like in accordance with necessity.

For mixing the particles (A) to (C), a known powder mixing method can be used. For example, a known powder mixing apparatus (for example, a horizontal cylindrical electric rolling mixer or a V- And then the particles (A) to (C) are added and mixed.

The order of introduction of the particle groups (A) to (C) into the powder mixing apparatus is not particularly limited and the particle groups (A) to (C) may be all put in the mixing apparatus in advance, A) to (C) may be sequentially added to the mixing apparatus in an arbitrary order and mixed. From the viewpoint of the fluidity of the particle group, it is preferable to mix the particle group (A) and the particle group (C) and then the particle group (B).

In addition to the particle groups (A) to (C), when any other particle group is to be blended, the other particle groups may be mixed with any one of the particle groups (A) to (C) (A) to (C) may be put in advance in a mixing apparatus, and these may be mixed. Further, after the particles (A) to (C) are mixed, liquid components such as an antioxidant may be added and mixed by spraying or the like.

However, from the viewpoint of the apparent solubility of the granular detergent composition, the amount of the water-insoluble component (zeolite or the like) to be used is within a range in which the content of the insoluble component in the granular detergent composition is less than 10% by mass with respect to the total mass of the granular detergent composition .

[Manufacturing method of particle group (A)] [

The particle group (A) containing an optional component such as a surfactant and, if necessary, a water-soluble inorganic salt can be produced by conventionally known methods.

For example, a part of the raw material (surfactant, optional component) constituting the particle group (A) is dispersed and dissolved in water to prepare a spray drying slurry (slurry preparing step), and the spray drying slurry is spray- To obtain spray dried particles (spray drying step). Subsequently, the obtained spray-dried particles are granulated together with the remaining raw materials (granulation step). Thereby, the particle group (A) can be obtained. Thereafter, the particle group (A) may be quartzed and adjusted to a desired average particle size and particle size distribution as required (quadrangle process).

During spray drying of the spray-drying slurry, hot gas is supplied into the spray-drying tower. The hot gas is supplied from, for example, the lower portion of the spray drying tower and discharged from the top of the tower of the spray drying tower. The temperature of this high-temperature gas is preferably 170 to 300 ° C, more preferably 200 to 280 ° C. If it is within this range, the spray-drying slurry can be sufficiently dried, and spray-dried particles having a desired water content can be easily obtained.

The temperature of the gas discharged from the spray drying tower is preferably 70 to 125 캜, and more preferably 70 to 115 캜.

In order to suppress the temperature of the obtained spray-dried particles from becoming too high when the high-temperature gas is supplied from the bottom of the spray-drying tower and discharged from the top of the tower of the spray-drying tower (countercurrent flow) Can be supplied. At the same time, for example, by introducing inorganic fine particles (zeolite or the like) or the like from the lower part of the spray drying tower and contacting the spray dried particles, it is possible to prevent the spray dried particles from adhering to the inner wall of the spray drying tower, The flowability of the obtained spray-dried particles can be improved. As the spray-drying tower, either a countercurrent or a co-current type may be used, and a countercurrent type is preferable because thermal efficiency and dry matter (spray-dried particles) can be sufficiently dried.

Examples of the apparatus for atomizing the spray-drying slurry include a pressure spray nozzle, a twin-fluid spray nozzle, and a rotary atomizer. Among them, it is preferable to use a pressure spray nozzle which can easily obtain a desired average particle diameter. Here, the &quot; pressure spray nozzle &quot; includes the entire nozzle used when spraying the spray-drying slurry by spraying while spraying the spray-drying slurry by applying pressure. Particularly, a nozzle having a structure in which a spray-drying slurry is guided from one or a plurality of inlets of the nozzle to a swirl chamber in the nozzle and has a structure for spraying the slurry as a swirl flow from the spray orifice in the swirl chamber is particularly preferable Do. The ignition time is preferably 2 to 4 MPa (gauge pressure), more preferably 2.5 to 3 MPa (gauge pressure).

Conventionally known methods can be used for the granulation process, and examples thereof include, for example, pulverization granulation, agitation granulation, electric transfer granulation, fluidized bed granulation, and the like, in which the spray dried granules and the remaining raw materials are milled and pulverized. For example, in the case of pulverizing and assembling, the pulverized pulverized product can be obtained by pulverizing the spray-dried particles and the remaining raw material, cutting the pulverized product while extruding it, and pulverizing the pulverized product.

As the quadrant process, for example, a plurality of kinds of eye sizes (such as open eyes) are prepared and laminated in the order of a sieve having a smallest eye size to form a sieve unit, And a method in which the particle group (A) is put on the upper part and the quartz unit is vibrated to quench. The particle group (A) remaining on each of the bodies is recovered per each body, and the recovered particle group (A) having a desired average particle size or particle size distribution can be obtained.

<Method of using granular detergent composition>

The granular detergent composition of the present invention can be used for washing the particulate matter.

Examples of the method of washing the particulate material using the granular detergent composition include a method of cleaning the object with a washing machine through a cleaning liquid having a concentration of the particulate detergent composition of 0.02 to 2 mass% or locking the object to the cleaning liquid , And conventionally known cleaning methods. Examples of the clothes include textiles such as medical care, cloth, curtain, and sheet.

[Example]

An embodiment of the present invention will be described in more detail. However, the present invention is not limited to these.

In each of the following examples, the following materials were used as raw materials.

[Particle group (A)]

MES: sodium salt of fatty acid methyl ester sulfonate having a carbon number of 16: carbon number of 18 = 80: 20 (mass ratio) (AI = 70%, the balance being unreacted fatty acid methyl ester, sodium sulfate, methylsulfate, hydrogen peroxide, Water, etc.).

LAS-Na: neutralized with a 48 mass% sodium hydroxide aqueous solution at the time of preparation of the surfactant composition, straight-chain alkyl (C 10-14) benzenesulfonic acid sodium salt (Lyphene LH-200 (96 mass% LAS- do).

C12 = 11.7% by weight, C14 = 0.4% by weight, C16 = 29.2% by weight, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight: 289).

Nonionic surfactant: LMAO-90 (trade name, manufactured by Lion Chemical) [polyoxyethylene (EO15 ^* ) alkyl (C12-14 ^* ) ether]. * &Quot; EO15 &quot; indicates that the average addition mole number of ethylene oxide is 15, and (C12-14) indicates that the alkyl group has 12 to 14 carbon atoms.

Sodium carbonate: granule ash, average particle diameter 320 占 퐉, bulk density 1.07 g / cm3, manufactured by Asahi Glass Co., Ltd.

Potassium carbonate: Potassium carbonate (powder), average particle diameter 490 占 퐉, bulk density 1.30 g / cm3, manufactured by Asahi Glass Co., Ltd.

Sodium sulfate: Neutral anhydrous sodium A0, manufactured by Shikoku Hosei Kogyo Co., Ltd.

MA: acrylic acid-maleic anhydride copolymer sodium salt, trade name; Aquarique TL-400, aqueous solution of 40 mass% of pure water, manufactured by Nippon Catalysts Co.,

· Zeolite: Type A zeolite, product name; Silton B, 80% by mass of pure water, manufactured by Mizusawa Chemical Co.,

· Fluorescent agent: Chinofol MS-GX (trade name, manufactured by BASF, bis (triazinylaminostilbene) disulfonic acid derivative, seminiferous (manufactured by BASF), distyrylbiphenyl derivative, water soluble fluorescent agent) Quasi - dispersible fluorescent agent) = 1/1.

[Particle group (B)]

(B) -1: sodium hydrogencarbonate particles, trade name, manufactured by Penrice; SODIUM BICARBONATE FOOD GRADE COARSE GRANULAR.

(B) -2: Sodium sulfate: Neutral anhydrous sodium AO, manufactured by Shikoku Hosei Kogyo Co., Ltd.

[Particles (C)]

(C) -1: Sodium palmitate (reagent, Kanto Chemical).

[Optional ingredients]

Sodium percarbonate (trade name: PC-W, manufactured by Nippon Perox Co., Ltd., effective oxygen content: 12.5%, average particle diameter: 850 탆)

Bleach activator: The bleach activator-containing granulate prepared in the following procedure (the blending amount shown in Table 4 below is the amount as the granulate).

The synthesis of sodium 4-dodecanoyloxybenzenesulfonate as a bleaching activator was carried out using sodium 4-hydroxybenzenesulfonate (reagent manufactured by Kanto Kagaku Co., Ltd.), N, N-dimethylformamide (manufactured by Kanto Kagaku Co., ), Lauric acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and acetone (reagent manufactured by Kanto Kagaku Co., Ltd.) in the following manner.

3000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate previously dehydrated was dispersed in 9000 g of N, N-dimethylformamide, and 3347 g (15.3 mol) of lauric acid chloride was stirred at 50 DEG C for 30 minutes while stirring with a steerer . After completion of dropwise addition, reaction was carried out for 3 hours, and N, N-dimethylformamide was distilled off at 100 DEG C under reduced pressure (0.5 to 1 mmHg). After washing with acetone, recrystallization was carried out in a solvent of water / acetone (= 1/1 mol)) and purification was performed to obtain crystals of sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90%.

70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate synthesized by the above-mentioned method, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)), and an alpha -olefin sodium sulfonate powder (Trade name) manufactured by Hosokawa Micron Co., Ltd. so as to have a total of 5000 g at a ratio of 5 parts by mass of a polypropylene resin (trade name: Liporan PJ-400 (manufactured by Lion Corporation)) and kneaded and extruded A 0.8 mmφ noodle-shaped extrusion product was obtained. This pressure product (60 ° C) was introduced into a Pitzmilk DKA-3 (trade name) manufactured by Hosokawa Micron Corporation, and 5 parts by mass of the A type zeolite powder was similarly supplied as a preparation and pulverized to obtain a bleaching activator Containing granules.

CMC: Carboxymethylcellulose (manufactured by Daicel Chemical Industries, Ltd., trade name: CMC Diesell 1190).

Enzyme (1): a mixture of Evarase 8T / Serucrin 4500T / Leifex 50T = 5/3/2 (by mass ratio), Novozymes Injection.

Enzyme (2): a mixture of Properase 4000D / Puraadax HA1200E / Manasta 375 = 5/3/2 (by mass), manufactured by Zenenkoa.

Flavoring agents: Flavoring compositions according to Tables 11 to 18 of JP-A-2002-146399.

· Coloring agent: Navy Blue (trade name, Ultramarine Blue, manufactured by Dainichiseika Color Ind. Co.).

(Examples 1 to 14, Comparative Examples 1 to 8)

The granular detergent compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were obtained by the following production methods A, B,

&Lt; Production method A (Examples 1 to 12 and Comparative Examples 1 to 8)

1. Preparation of Particle Group (A)

(1) to (3) were carried out under any of the production conditions (1) to (6) shown in Table 2 according to the A-particle composition A- .

Step (1)

A part of nonionic surfactant (amount of 25 mass% based on MES) was added to an aqueous slurry of MES (prepared to have a water concentration of 25 mass%) obtained by sulfonating fatty acid ester as a raw material and neutralizing, Was concentrated to a concentration of 11 mass% under reduced pressure using a thin film drier to obtain a mixed concentrate of MES and a nonionic surfactant.

Step (2)

Water was added to the jacket-equipped mixing vessel equipped with the stirring device, and the temperature was adjusted to 80 캜. To this, a surfactant other than MES and nonionic surfactant was added and stirred for 10 minutes. Subsequently, MA agent was added. After stirring for 10 minutes, a portion of the zeolite A (amount excluding 1.0 mass% for addition at the time of milling and 5.0 mass% for milling additive to be added in the following step (3) from the compounding amount described in Table 1 below), sodium carbonate, Potassium carbonate and sodium sulfate were added. The resulting mixture was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass (slurry preparation operation), followed by spray drying using a countercurrent spray drying tower under the condition of a hot air temperature of 280 캜 to obtain an average particle size of 320 탆 and a bulk density of 0.30 g / cm &lt; 3 &gt;, and water content of 6 mass% (spray operation).

Step (3)

The obtained spray-dried particles, the mixed concentrate obtained in the step (1), the 1.0 mass% of the zeolite A, the nonionic surfactant (the remainder excluding the nonionic surfactant in the mixed concentrate), the fluorescent agent, (KRC-S12 type, manufactured by Kurimoto Ironworks Co., Ltd.), and then milled under the conditions of the number of revolutions of the kneader of Xrpm and the jacket temperature of 60 캜 to obtain a 7% by mass moisture content of the raw material containing the surfactant ). The cargo was cut with a cutter (the cutter circumferential speed was 5 m / s) while extruding the cargo on the same day with a Pelter-Double (EXDFJS-100 type, manufactured by Fuji Paper Industries Co., Ltd.) equipped with a die having a hole diameter of 10 mm, To obtain a pellet-shaped product having a size of about 30 mm.

Subsequently, 5.0 mass% of A-type zeolite as a pulverizing assistant was added to the obtained pellet-shaped product, and the resulting mixture was melt-kneaded with Fitz mill (DKA- 3), and the particle group A was obtained (assembly operation). The granules A were obtained by crushing (screen hole diameter Y mm: first stage / second stage / third stage, rotation speed Zrpm: first stage / second stage / third stage).

The manufacturing conditions of each example (the number of revolutions (X) of the kneader, the screen hole diameter (Y) and the number of revolutions (Z) of the Pitzmill) were as shown in Table 2.

The average particle size (R), the half width (m), the bulk density (a), and the applied production conditions of the particle group (A) obtained in each example are shown in Tables 3 to 5.

[2. Preparation of granular detergent composition]

Particles (A) to (C), sodium percarbonate and CMC were simultaneously charged into a vessel rotating cylindrical mixer at a rate of 15 kg / min and mixed according to the compositions shown in Tables 3 to 5 below. The container rotary type cylindrical mixer has a container having a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, a height of 0.15 m at the outlet opening (weir), a bladed wing of 0.1 m in height and 1.4 m in length, It is the specification attached with the sheet. Also, the number of revolutions of the inner mixing blades was adjusted so that the number of plies was Fr = 0.2.

For the group of particles fluidized by rotating the container, the powder was sprayed and transferred for 1 minute. In order to color a part of the obtained detergent composition precursor, the particles were transferred to a belt conveyor at a speed of 0.5 m / s (30 mm in height of the surfactant-containing particle layer on the belt conveyor and 300 mm in width) % Water dispersion.

Using the above container rotation type cylindrical mixer, a granular detergent composition was obtained by mixing the detergent composition precursor partially colored with the enzyme under the same conditions as above for 5 minutes.

&Lt; Production method B (Example 13) >

A particle group (A) was obtained in the same manner as in the preparation of the particle group (A) in the production method A except that the MES and the nonionic surfactant were not used. The A particle composition of the obtained particle group (A) was A-2 shown in Table 1, and the production conditions were (7) shown in Table 2. Table 4 shows the average particle diameter (R), the half width (m), the bulk density (a), and the applied conditions of the obtained particle group (A). Subsequently, according to the composition shown in Table 4, the particle groups (A) to (C), sodium percarbonate, bleaching activator and CMC were simultaneously charged into a vessel rotating cylindrical mixer at a rate of 15 kg / min and mixed. Thereafter, a granular detergent composition was obtained in the same manner as in the preparation of the granular detergent composition in Production Method A.

&Lt; Production method C (Example 14) >

A particle group (A) was obtained in the same manner as in the production of the particle group (A) in Production Method A, except that MES and a fluorescent agent were not used. The A particle composition of the obtained particle group (A) was A-3 shown in Table 1, and the production conditions were (8) shown in Table 2. Table 4 shows the average particle diameter (R), the half width (m), the bulk density (a), and the applied conditions of the obtained particle group (A).

Subsequently, according to the composition shown in Table 4, the particle groups (A) to (C) and the CMC were simultaneously charged and mixed in a vessel rotating cylindrical mixer at a rate of 15 kg / min. Thereafter, a granular detergent composition was obtained in the same manner as in the preparation of the granular detergent composition in Production Method A.

In order to prepare the above granular detergent composition, as a particle group (B), quartz of commercial products (eye size 500 탆, 425 탆, 355 탆, 300 탆, 250 탆, 212 탆, 150 탆, 75 占 퐉 and 53 占 퐉), and they were used in an amount required (to have a predetermined average particle diameter and half width), mixed and used.

Tables 3 to 5 show the kind, average particle diameter (r), half width (n) and bulk density (b) of the particle group (B) used in each example. Also, the value of r / 5 is listed. (B) -1 represents sodium hydrogencarbonate, and (B) -2 represents sodium sulfate.

As the particle group (C), particles having a predetermined particle diameter were used as they were. Tables 3 to 5 show the types of the particle group (C) used in each example. In the table, (C) -1 represents sodium palmitate.

&Lt; Evaluation of granular detergent composition >

The obtained granular detergent composition was evaluated as follows. The results are shown in Tables 3 to 5.

[Evaluation of Solubility]

Twelve cotton T-shirts were put into the automatic washing machine (AW-80VC manufactured by TOSHIBA CO., LTD.), And three folded T-shirts, three polyester shirts and three acrylic shirts were put on the cloth, 47 g of granular detergent composition prepared in the center of water was loaded, and further, 3 sheets of cotton T-shirt, 3 sheets of polyester shirt, and 3 sheets of acrylic shirt were put. The amount of water (water amount) 47 liters (tap water at 5 ° C), 10 minutes of washing, 4 minutes of dehydration, and the amount of water remaining in the washing machine and the amount remaining after being dissolved in the naked eye were measured according to the following evaluation criteria Respectively. In addition, the substrate was black-based so that the total amount was about 4 kg. The results are shown in Tables 3 to 5. Considering the usability at home, the solubility in water was judged as &quot; Good &quot; and &quot; Good &quot;.

[Evaluation standard]

◎: There is almost nothing left to melt.

○: Melting A slight level is seen, but no problem level.

△: It is conspicuous that it is melted.

X: Remained melted. Remarkable.

[Evaluation of apparent melting ability of powder]

The granular detergent composition was packed in a paper container (9 cm x 15 cm x 12 cm) at 1 kg to prepare a granular detergent product. With regard to the granular detergent product, the image of the ease of melting of the powder felt when 10 persons had seen the powder (granular detergent composition) in the paper container and when the powder was discharged with the measuring spoon was evaluated in the following five steps, The average point was calculated. The results (average points) are shown in Tables 3 to 5. The average score was 3.5 or better.

[Evaluation standard]

5 points: It feels like melting very well.

4 points: It feels like melting well.

3 points: It feels like melting normally.

2 points: I feel like melting a little.

1 point: I feel like it is difficult to melt.

[Evaluation of liquidity]

The granular detergent composition was packed in a paper container (9 cm x 15 cm x 12 cm) at 1 kg to prepare a granular detergent product. About the granular detergent product, ten panelists were evaluated in five steps of making flakes (granular detergent composition) in a paper container put on a measuring spoon, and the average point was calculated. The results (average points) are shown in Tables 3 to 5. The average score was 3.5 or better.

[Evaluation standard]

5 points: It is very easy to bounce by the boss.

4 points: It is relatively easy to bounce.

3 points: You can go to normal without any problems.

2 points: I do not feel a bit nervous and it is hard to get out.

1 point: It does not feel like a boss and it is hard to bounce.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

As shown in the above results, the granular detergent compositions of Examples 1 to 14 were less soluble in washing, had good solubility in water, and seemed to melt easily. Also, the fluidity was good and the feeling of use was excellent.

On the other hand, Comparative Example 1 in which r / R was 0.45 or less did not satisfy the formula (1) had poor solubility in water. Comparative Example 2 in which r / R was 1.00 or more and did not satisfy formula (1) had poor solubility in water.

Comparative Example 3 in which X / Y did not satisfy Formula (a × R ³ ) / (br ³ ) × 0.3 (= 2.6) or less was poor in solubility in water. Comparative Example 4 in which X / Y was not satisfied with (a × R ³ ) / (b × r ³ ) × 3.0 (= 5.5) or more was poor in water solubility.

Comparative Example 5 in which n / m was 0.40 or less and Comparative Example 6 in which n / m was 1.10 or more and did not satisfy Formula (3) all had poor solubility in water.

Comparative Example 7, which did not contain the particle group (C), had poor solubility in water and poor fluidity.

Comparative Example 8, in which the average particle size of the particle group (C) was larger than r / 5, was poor in water solubility and fluidity was lower than those of Examples 1 to 14,

Claims (1)

(A) containing a surfactant, a particle group (B) comprising a water-soluble inorganic salt, and a particle group (C) comprising a water-soluble saturated fatty acid salt,
A granular detergent composition which satisfies the following formulas (1) to (5).
0.45 &lt; r / R &lt; 1.00 ... (One)
(a × R ³ ) / (b × r ³ ) × 0.3 <X / Y <(a × R ³ ) / (b × r ³ ) (2)
70? X + Y &lt; 100 ... (3)
0.40 &lt; n / m &lt; 1.10 ... (4)
s? r / 5 ... (5)
Note that the symbols in the expressions (1) to (5) have the following meanings.
R: Average particle size (탆) of the above-mentioned particle group (A).
r: average particle diameter (占 퐉) of the particle group (B).
a: bulk density (g / cm3) of the above-mentioned particle group (A).
b: bulk density (g / cm &lt; 3 &gt;) of the particle group (B)
X: Content (mass%) of the above-mentioned particle group (A).
Y: content (mass%) of the above-mentioned particle group (B).
m is the half width (占 퐉) of the particle size distribution of the particle group (A).
n is the half width (占 퐉) of the particle size distribution of the particle group (B).
s: average particle diameter (占 퐉) of the particle group (C).

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