JP2016069394A - Granular detergent, method for producing the same and detergent product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granular detergent capable of suppressing discoloration such as yellow discoloration, a method for producing the same, and a detergent product.SOLUTION: Provided is a granular detergent obtained by powdery mixing a particle group (A) containing a surfactant and a particle group (B) of the single crystal particles of a water-soluble inorganic salt, and satisfies the following formula (1): 0.45<r/R<1.00(1); where, the R in the formula (1) denotes the average particle diameter (μm) of the particle group (A), and the r in the formula (1) denotes the average particle diameter (μm) of the particle group (B).SELECTED DRAWING: None

Description

  The present invention relates to a granular detergent, a method for producing the same, and a detergent product.

Conventionally, granular detergents are generally used for washing clothes and the like. The granular detergent may cause discoloration such as yellowing during storage. When discoloration occurs in the granular detergent, the beauty of the detergent product may be impaired and the commercial value may be reduced.
To solve the problem of discoloration of the granular detergent, for example, Patent Document 1 discloses that yellowing of the granular detergent can be suppressed by replacing nitrogen gas when packaging the granular detergent.

JP 2001-122344 A

In recent years, granular detergents have been filled in refill containers such as pouches from the viewpoint of resource saving. The granular detergent filled in an irregular container such as a pouch is more likely to cause discoloration such as mottled yellowing.
However, with the technique disclosed in Patent Document 1, yellowing of the granular detergent may not be sufficiently suppressed. In addition, it is necessary to introduce new equipment for replacing nitrogen gas.
Therefore, it is calculated | required that the discoloration which arises in granular detergent is suppressed by the composition.

  This invention is made | formed in view of the said situation, and aims at the granular detergent which can suppress discoloration, such as yellowing.

As a result of intensive studies, the present inventors have found that the following granular detergent can solve the above problems.
That is, the present invention has the following configuration.
[1] A particle group (A) containing a surfactant and a particle group (B) of single crystal particles of a water-soluble inorganic salt are powder-mixed to satisfy the following formula (1): Granular detergent.
0.45 <r / R <1.00 (1)
However, R in Formula (1) is the average particle diameter (μm) of the particle group (A), and r in Formula (1) means the average particle diameter (μm) of the particle group (B). To do.
[2] A detergent product, wherein the granular detergent according to [1] is filled in a container.
[3] The detergent product according to [2], wherein the container is an irregular container.
[4] The method for producing a granular detergent according to [1], comprising a step of powder-mixing the particle group (A) and the particle group (B). Manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the granular detergent in which discoloration, such as yellowing, was suppressed, and its manufacturing method can be provided.

It is a schematic diagram for demonstrating Formula (1). It is a graph of the particle size distribution for demonstrating Formula (4). It is a graph of the particle size distribution for demonstrating Formula (4). It is the photograph which observed the particle group (B) of the single crystal particle of sodium hydrogencarbonate with a microscope. It is the photograph which observed the particle group (B ') of the polycrystalline particle of sodium hydrogencarbonate with a microscope.

The granular detergent of the present invention is a composition obtained by powder mixing a particle group (A) containing a surfactant and a particle group (B) of a single crystal particle of a water-soluble inorganic salt, and the following The expression (1) is satisfied.
0.45 <r / R <1.00 (1)
However, R in Formula (1) is the average particle diameter (μm) of the particle group (A), and r in Formula (1) is the average particle diameter (μm) of the particle group (B). means.

In the present invention, the average particle diameter is a volume-weighted average diameter (arithmetic average particle diameter in volume% mode) in a particle size distribution (volume-based frequency distribution) measured by a laser diffraction / scattering method. D = Σn _i x _i ⁴ / Σn _i x _i ³ (x _i = channel center value, n _i = percentage of particles in the i th channel). The 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, Inc.).

  Here, although the detail of the reason why yellowing occurs in the granular detergent is not clear, the granular detergent of the present invention can suppress yellowing during storage by satisfying the above formula (1).

The above formula (1) shows the relationship between the average particle diameter R of the particle group (A) and the average particle diameter r of the particle group (B).
In the formula (1), 0.45 <r / R <1.00, and preferably 0.55 <r / R <0.90. When r / R exceeds 0.45, it becomes easy to suppress aggregation of A particles in the granular detergent.

This is because the particles of the particle group (B) (hereinafter also referred to as B particles) function as a spacer, so that the contact between the particles of the particle group (A) (hereinafter also referred to as A particles) decreases. It is considered that the contact between the A particles can be suppressed.
Explaining schematically with reference to FIG. 1, when the particle group (A) is arranged so that four A particles are in contact with each other in the vertical direction and two in the horizontal direction on the plane, four A particles are present. Gaps are formed between the particles. B particles having a diameter r of [distance between the centers of two opposing A particles −R / 2 × 2] or less can enter the gap. At this time, r / R is about 0.41.
When r / R is more than 0.45, as shown in FIG. 1B, the B particles serve as spacers, and the contacts between the A particles decrease.
When r / R is 0.41 or less, as shown in FIG. 1 (a), B particles enter the gaps between the A particles. Therefore, the contact points of the plurality of A particles are the same as when there are no B particles. It is. Moreover, when r / R is more than 0.41 and 0.45 or less, even if B particles enter, the contacts between the A particles hardly decrease.
When r / R is 1.00 or more, the B particles function as a spacer, but the number of B particles is relatively reduced by increasing the mass per one B particle, and the contact point between the A particles is reduced. There is a possibility that it cannot be reduced sufficiently.

The granular detergent of the present invention preferably further satisfies any one or more of the following formulas (2) to (4), and more preferably satisfies all of the following formulas (2) to (4).
{(A × R ³ ) / (b × r ³ ) × 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)
However, the symbols in the formulas (2) to (4) have the following meanings.
a: Bulk density (g / cm ³ ) of the particle group (A).
b: Bulk density (g / cm ³ ) of the particle group (B).
X: Content (mass%) of the particle group (A).
Y: Content (mass%) of the particle group (B).
m: Half width (μm) of the particle size distribution of the particle group (A).
n: Half width (μm) of the particle size distribution of the particle group (B).

Here, the bulk density is a value measured according to JIS K3362 (2008).
The half-value width of the particle size distribution is the peak width at a position half the height of the peak top of the particle size distribution (horizontal axis: particle diameter (μm), vertical axis: frequency (%)) measured as described above. Indicates.

Formula (2) is expressed as {(a × R ³ ) / (b × r ³ ) × 0.3} <{X / Y} <{(a × R ³ ) / (b × r ³ ) × 3.0 }.
When X / Y is more than 0.3 times (a × R ³ ) / (b × r ³ ) and less than 3.0 times, the balance between the number of A particles and the number of B particles in the granular detergent is good, In the granular detergent, the B particles are more likely to act as a spacer.
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.
That is, the mass per A particle is obtained by a × 4 / 3π × (R / 2 × 10 ⁻⁴ ) ³ . Therefore, when the number of A particles in the granular detergent is p, X can also be expressed as {a × 4 / 3π × (R / 2 × 10 ⁻⁴ ) ³ } × p. Similarly, the mass per B particle is determined by b × 4 / 3π × (r / 2 × 10 ⁻⁴ ) ³ , so when the number of B particles in the granular detergent is q, Y is , {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 this equation is summarized as (a × R ³ ) / (b × r ³ ) × (p / q). When this is replaced with X / Y in the equation (2) and deformed, 0.3 <p / q <3.0 is obtained and an equation indicating the relationship between p and q is obtained.
As described above, the B particles are considered to function as a spacer by entering between the particles of the particle group (A), and the B particles are included in the number of particles satisfying 0.3 <p / q <3.0. Therefore, it becomes easier to act as a spacer.

In the formula (3), 70 ≦ X + Y ≦ 100, 80 ≦ X + Y <100 is preferable, and 90 ≦ X + Y <100 is particularly preferable.
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) is 70% by mass or more, good solubility of the granular detergent in water is easily obtained, Detergency as a granular detergent is also easier to increase.

In the formula (4), 0.40 <n / m <1.10, and 0.60 <n / m <1.10 is preferable.
Formula (4) shows the relationship between the size of the particle size distribution of the particle group (A) and the size of the particle size distribution of the particle group (B).
A specific example will be described with reference to FIGS. FIG. 2 shows the particle size distribution of one kind of particle group (A), two kinds of particle groups (B) having the same average particle diameter and different n (particle group (B1) having a half width of n1, and a half width of It is an example of the graph which piled up the particle size distribution of the particle group (B2)) of n2.
FIG. 3 is a graph showing the particle size distribution of the particle group (A) having the same average particle diameter and m being narrower than the particle size distribution of the particle group (A) in FIG.
As shown in these figures, when the half-value widths m and n are increased, the proportion of particles whose particle diameter is deviated from the average particle diameter increases, and the deviation also increases. Therefore, even if the average particle diameter satisfies the formula (1), n / m is 1.10 or more (the particle size distribution of the particle group (B) is wider than the particle size distribution of the particle group (A)), or The particle size distribution of the particle group (A) is narrower than the particle size distribution of the particle group (B)), and the proportion of B particles that do not satisfy the formula (1) and become spacers at the individual particle level increases.
On the other hand, n / m is 0.40 or less (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 the particle group (B ) Is larger than the particle size distribution of (), the proportion of A particles in which B particles are not spacers increases.
By satisfying the formula (4), there are a sufficient number of B particles serving as spacers with respect to the A particles, the number of contact points between the A particles can be further reduced, and aggregation of the A particles can be more easily suppressed. .
Next, the components contained in the granular detergent of the present invention will be described in detail.

<Particle group (A)>
The particle group (A) is a particle group containing a surfactant.

[Surfactant]
The surfactant is not particularly limited, and a surfactant blended in a granular detergent or the like can be used, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. .

The anionic surfactant is not particularly limited as long as it is used for the granular detergent, and examples thereof include the following.
(1-1) α-sulfo fatty acid alkyl ester salt.
The kind of α-sulfo fatty acid alkyl ester salt is not particularly limited, and any α-sulfo fatty acid alkyl ester salt used in general granular detergents can be suitably used, and is represented by the following formula (11). Those are preferred.
R ¹¹ —CH (SO ₃ M) —COOR ¹² (11)

In formula (11), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, preferably 14 to 16 carbon atoms, or a linear or branched alkenyl group having 8 to 20 carbon atoms. It is.
R ¹² is an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable.
M represents a counter ion, and examples thereof include alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Of these, alkali metal salts are preferred.
As the α-sulfo fatty acid alkyl ester salt, for example, α-sulfo fatty acid methyl ester sodium salt (MES) is preferable.

(1-2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(1-3) Alkanesulfonate having 10 to 20 carbon atoms.
(1-4) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(1-5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(1-6) 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) is An alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 5 to 10 moles.
(1-7) 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 3 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 30 moles.
(1-8) 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) is An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 5 to 10 moles.
(1-9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(1-10) Monoalkyl, dialkyl or sesquialkyl phosphates having an alkyl group having 10 to 20 carbon atoms.
(1-11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(1-12) 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.
These anionic surfactants may be used alone or in a combination of two or more.

The nonionic surfactant is not particularly limited as long as it is conventionally used for granular detergents, and examples thereof include the following.
(2-1) 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 to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Added 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.
(2-2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(2-3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(2-4) Polyoxyethylene sorbitan fatty acid ester.
(2-5) Polyoxyethylene sorbite fatty acid ester.
(2-6) Polyoxyethylene fatty acid ester.
(2-7) Polyoxyethylene hydrogenated castor oil.
(2-8) Glycerin fatty acid ester.

Examples of the fatty acid alkyl ester alkoxylate (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 (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. ]

In formula (31), OA is preferably ethylene oxide having 2 carbon atoms, q is preferably 5 to 30, more preferably 9 to 25, still more preferably 12 to 23, and particularly preferably 14 to 20.
R ¹⁰ is preferably a methyl group.

These nonionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
Among the nonionic surfactants, the nonionic surfactant of (2-1) is preferable, and in particular, an average of 5 to 30 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 12 to 16 carbon atoms. Preferred are polyoxyalkylene alkyl (or alkenyl) ethers. Among polyoxyalkylene alkyl (or alkenyl) ethers, polyoxyethylene added with an average of 5 to 30 mol, preferably an average of 9 to 25 mol, more preferably an average of 12 to 23 mol, and particularly preferably an average of 14 to 20 mol. Ethylene alkyl (or alkenyl) ether is preferred.
Further, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and 9 to 16 HLB, fatty acid methyl ester in which ethylene oxide is added to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
In addition, HLB of nonionic surfactant in this specification is a value calculated | required by the method of Griffin (Yoshida, Shindo, Ogaki, Yamanaka co-edit, "New edition surfactant handbook", Kogyoshosho, 1991). Year, page 234).
The melting point in the present specification is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.

Examples of the cationic surfactant include the following.
(3-1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(3-2) Mono long chain alkyl tri-short chain alkyl type quaternary ammonium salt.
(3-3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

One of these surfactants may be used alone, or two or more thereof may be used in combination.
Among the above, the particle group (A) preferably contains an anionic surfactant, and at least one selected from α-sulfo fatty acid alkyl ester salts and LAS salts from the viewpoint of detergency. It is preferable to contain. Further, the content of at least one selected from α-sulfo fatty acid alkyl ester salt and LAS salt in the anionic surfactant is preferably 50% by mass or more, and more preferably 60% by mass or more.

The particle group (A) also preferably contains a nonionic surfactant as a surfactant. As the nonionic surfactant, for example, the above-mentioned (2-1) nonionic surfactant (polyoxyalkylene alkyl (or alkenyl) ether) is preferable.
When an anionic surfactant and a nonionic surfactant are used in combination, the mass ratio (anionic surfactant / nonionic surfactant) in the particle group (A) is determined from the viewpoint of detergency and re-contamination prevention properties. 1-10 are preferable, 2-6 are more preferable, and 3-5 are more preferable.

  The content of the surfactant in the particle group (A) is not particularly limited, but is 10 to 30% by mass with respect to the total mass of the particle group (A) in terms of manufacturability and adhesion between particles. Is preferable, 12 to 28 mass% is more preferable, and 14 to 25 mass% is particularly preferable.

Moreover, when a particle group (A) contains a C10-20 higher fatty acid salt, 1-10 mass% is preferable with respect to the total mass of a particle group (A), and 3-8 mass% is more. preferable.
When the content of the higher fatty acid salt having 10 to 20 carbon atoms is equal to or higher than the lower limit, the cleaning performance and the shape retention of the granular detergent can be further improved. Moreover, it becomes easy to suppress yellowing of a granular detergent as content of a C10-C20 higher fatty acid salt is below the said upper limit.

[Water-soluble inorganic salt]
The particle group (A) preferably contains a water-soluble inorganic salt in addition to the surfactant in terms of fluidity and manufacturability of the particles.
As the water-soluble inorganic salt, water-soluble inorganic salts usually used for granular detergents and the like as a detergency builder can be used. For example, alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium hydrogen carbonate, potassium hydrogen carbonate, Alkali metal hydrogen carbonates such as sodium sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate (for example, trade name “Na-SKS-6” (δ-Na manufactured by Clariant Japan) _{2 O} · 2SiO ₂₎ crystalline alkali metal silicates, etc.), amorphous alkali metal silicates; pyrophosphate; alkali metal chloride such as sodium chloride, potassium chloride; sodium sulfate, sulfates such as potassium sulfate Salt, tripolyphosphate, orthophosphate, metaphosphate, hexametaphosphate, phytate, etc. Phosphate; compound of sodium and amorphous alkali metal silicate carbonate (e.g., company Rhodia NABION15 (trade name)), and the like.
These water-soluble inorganic salts may be used alone or in combination of two or more.

Among the above, the water-soluble inorganic salt contained in the particle group (A) is preferably an alkali metal carbonate or sulfate, and more preferably sodium carbonate, potassium carbonate, or sodium sulfate. Any one of these may be used alone or two or more of them may be used in combination.
Among the above, it is preferable to use sodium carbonate and sodium sulfate in combination. By using sodium carbonate and sodium sulfate in combination, the strength and fluidity of the particle group (A) tend to increase.
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, and more preferably 1.5 to 10. When the mass ratio of sodium carbonate / sodium sulfate is 1 or more, the detergency of the particle group (A) tends to be further improved, and when it is 10 or less, the strength and fluidity of the particle group (A) are more excellent. .
In addition, as sodium carbonate and sodium sulfate, anhydrides are preferably used. In the present specification, the descriptions of “sodium carbonate” and “sodium sulfate” refer to an anhydride.

  The content of the water-soluble inorganic salt in the particle group (A) is not particularly limited, but the mass ratio of the water-soluble inorganic salt to the surfactant in the particle group (A) (water-soluble inorganic salt / surfactant) Is preferably in the range of 1-5. The water-soluble inorganic salt / surfactant is more preferably 2 to 4, and further preferably 2 to 3. When the water-soluble inorganic salt / surfactant is within the above range, the granular detergent produced using the particle group (A) is excellent in solubility in water, and the initial and temporal fluidity are also improved. Cheap. Further, when the water-soluble inorganic salt / surfactant is 1 or more, an excellent detergency can be obtained while keeping the surfactant concentration low. Further, when the water-soluble inorganic salt / surfactant is 5 or less, it is easy to produce (granulate) the particle group (A).

[Other optional ingredients]
The particle group (A) may further contain other components than the surfactant and the water-soluble inorganic salt, if necessary. As the other components, known components blended in granular detergents can be used, such as organic builders, water-insoluble inorganic salts, fluorescent brighteners, polymers, enzyme stabilizers, anti-caking agents, reducing agents, Examples include metal ion scavengers and pH adjusters.

Examples of the water-insoluble inorganic salt include zeolite and clay mineral.
Among these, zeolite is preferably used as a builder that contributes to an improvement in detergency. Zeolite is a general term for aluminosilicate, and both a crystalline and amorphous (amorphous) can be used as the aluminosilicate. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred. 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% by mass, more preferably 3 to 15% by mass, and more preferably 5 to 10% by mass with respect to the total mass of the particle group (A). % Is more preferable. When it is at least the lower limit of the above range, the effect of improving the detergency due to the use of zeolite is easily obtained, and when it is at most the upper limit, deterioration of rinsing properties due to the use of zeolite is difficult to occur.

[Average particle size]
The average particle diameter R of the particle group (A) can be appropriately set within the range satisfying the formula (1), and is not particularly limited, but is preferably 100 to 500 μm, more preferably 100 to 300 μm, and further preferably 100 to 250 μm. Preferably, 100-200 micrometers is especially preferable.
When the average particle diameter of the particle group (A) is not more than the above upper limit, the time required for dissolution of the A particles is short and the solubility is good. Moreover, when average particle diameter R becomes small, the average particle diameter of particle group (B) will also become small relatively, and the average particle diameter of the whole granular detergent will become small. Therefore, the dissolution time of the whole granular detergent is shortened, and an image that the user can easily dissolve can be given.
When the average particle diameter of the particle group (A) is less than 100 μm, the average particle diameter of the particle group (B) becomes very small to satisfy the formula (1), and the handleability is lowered.

[Half width of particle size distribution]
The full width at half maximum m of the particle size distribution of the particle group (A) is not particularly limited, but is preferably set as appropriate within a range satisfying the formula (4).

[The bulk density]
Although the bulk density a of a particle group (A) is not specifically limited, 0.6-1.2 g / cm < ³ > is preferable and 0.8-1.0 g / cm < ³ > is more preferable.

[amount of water]
Although the moisture content of particle group (A) is not specifically limited, 4-10 mass% is preferable, 5-9 mass% is more preferable, 5.5-8.5 mass% is further more preferable. If the water content is 4% by mass or more, the solubility in water is good, and if it is 10% by mass or less, the fluidity after storage is good.
The moisture content is a value measured as an evaporated volatile content after heating at 130 ° C. for 20 minutes with an infrared moisture meter (for example, a Kett moisture meter manufactured by Kett Scientific Laboratory).

[Blending amount]
The compounding amount X of the particle group (A) in the granular detergent is not particularly limited, but is preferably set as appropriate within a range satisfying the formula (2) and the formula (3). The blending amount X is preferably 50% by mass or more and more preferably 60% by mass or more with respect to the total mass of the granular detergent. Good detergency can be obtained when the content is 50% by mass or more. In consideration of the balance with other components, the upper limit of the amount X is preferably 90% by mass or less, and more preferably 85% by mass or less.

<Particle group (B)>
The particle group (B) is a particle group of single crystal particles of a water-soluble inorganic salt.
Here, the single crystal particles of the water-soluble inorganic salt are those in which the B particles are one crystal and exist independently, and are distinguished from the polycrystallized coalescent particles (polycrystalline particles). .
Single crystal particles of a water-soluble inorganic salt have higher particle strength and are less likely to be destroyed than polycrystalline particles.

The granular detergent is usually filled and stored in a container such as a carton, and the water-soluble inorganic salt particles are destroyed and refined at the bottom and corners of the container by the pressure of the granular detergent due to its own weight.
In particular, when granular detergent is filled in an irregular shaped container such as a pouch, in addition to its own weight as described above, containers are stacked and stored during transportation or at the store, or held by people. Thus, a large pressure is applied to the granular detergent, and the particles of the water-soluble inorganic salt are easily refined.

Since the particle group (B) of the present invention is composed of single crystal particles of a water-soluble inorganic salt, miniaturization of the particles is suppressed, and the average particle diameter r of the particle group (B) is easily kept constant.
Therefore, the granular detergent of the present invention can satisfy the above formula (1) even during storage and can suppress discoloration such as yellowing.

  Whether the particle group (B) is a particle group of single crystal particles or a particle group of polycrystalline particles can be easily determined from appearance observation using a microscope, X-ray diffraction measurement, or the like.

As an example, FIG. 4 shows a particle group (B) of sodium hydrogen carbonate single crystal particles, and FIG. 5 shows a photograph of a particle group (B ′) of sodium hydrogen carbonate particles observed with a microscope. Show.
As shown in FIGS. 4 and 5, the external appearances of the two are clearly different, so that they can be easily discriminated from external observations using a microscope or the like.
Moreover, since the single crystal particle shows a strong reflection intensity in the X-ray diffraction measurement, it is possible to discriminate both by the X-ray diffraction measurement. In the wide-angle X-ray diffraction measurement, the single crystal particle group (B) of the present invention has, for example, a single crystal particle group of sodium sulfate having a strongest reflection intensity exceeding 2000, while being polycrystalline. The particle group of particles has the strongest reflection intensity of about 1500. The particle group of sodium hydrogen carbonate single crystal particles has the strongest reflection intensity exceeding 5000, while the particle group of polycrystalline particles has the strongest reflection intensity of about 1500. The single crystal particle group of sodium carbonate has the strongest reflection intensity exceeding 4000, while the particle group of polycrystalline particles has the strongest reflection intensity of about 1500.
The reflection intensity was measured using a sample obtained by removing fine particles of 150 μm or less from the particle group (B) and the particle group (B ′) with a sieve. Pert-Pro MPD "), and X-ray output: 40 mA, 45 kV, measurement angle 2θ: 30.4 °.

As the water-soluble inorganic salt in the particle group (B), water-soluble inorganic salts usually used in granular detergents and the like as a detergency builder can be used. For example, alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal sulfites such as sodium and potassium sulfite; alkali metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and sodium sesquicarbonate; alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride and chloride Examples include alkali metal chlorides such as potassium; phosphates such as pyrophosphate, tripolyphosphate, orthophosphate, metaphosphate, hexametaphosphate, and phytate.
Among these, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and sodium sesquicarbonate are preferable, and sodium hydrogen carbonate is particularly preferable in terms of solubility and detergency.
The B particles constituting the particle group (B) may be one type or two or more types. When using 2 or more types of B particle | grains together, it is preferable to use the thing of the same particle size distribution as each B particle | grain.
Moreover, it is preferable to use a B particle having a high particle strength.

In the present invention, a particle group obtained by attaching a fragrance to a particle group of single crystal particles of a water-soluble inorganic salt may be used as the particle group (B) within a range satisfying the formula (1).
Generally, perfumes contain components that are easily oxidized and can cause yellowing. However, when perfumes are adhered to a group of single crystal particles of a water-soluble inorganic salt and blended with granular detergent, It becomes easy to suppress the yellowing of the detergent.
Moreover, when attaching a fragrance | flavor to the said particle group, in order to improve the adhesiveness, you may make a coating agent, such as nonionic surfactant, adhere simultaneously with a fragrance | flavor.
The content of the single crystal particles of the water-soluble inorganic salt in the particle group (B) is preferably 80% by mass or more, and more preferably 90% by mass or more.

Although it does not specifically limit as said fragrance | flavor, For example, what contains the fragrance | flavor component described in Paragraph [0010] of Unexamined-Japanese-Patent No. 2012-140555 is mentioned. Moreover, it is preferable that the said fragrance | flavor contains 20 weight% of compounds which have any one or both of a hydroxyl group and a carboxy group from the point which improves fragrance standing. Examples of the compound having one or both of the hydroxyl group and the carboxy group include the compounds described in paragraph [0012] of the above publication.
The nonionic surfactant is not particularly limited, and examples thereof include nonionic surfactants used in the particle group (A) of the present invention.

The mass ratio of the fragrance to the water-soluble inorganic salt in the particle group (B) [fragrance / water-soluble inorganic salt] is preferably 1/80 to 1/6, more preferably 1/50 to 1/10, and 1/30. -1/20 is more preferable.
The mass ratio of the nonionic surfactant to the water-soluble inorganic salt in the particle group (B) [nonionic surfactant / water-soluble inorganic salt] is preferably 1/80 to 1/6, and preferably 1/50 to 1/10. More preferred is 1/30 to 1/20.

[Average particle size]
The average particle diameter r of the particle group (B) can be appropriately set in consideration of the average particle diameter R of the particle group (A) within the range satisfying the formula (1), but is preferably 45 to 400 μm, 55-300 micrometers is more preferable and 100-200 micrometers is especially preferable.

[Half width of particle size distribution]
The full width at half maximum n of the particle size distribution of the particle group (B) is not particularly limited, but is preferably set within a range satisfying the formula (4).

[The bulk density]
Although the bulk density b of particle group (B) is not specifically limited, 0.6-1.7 g / cm < ³ > is preferable and 0.8-1.5 g / cm < ³ > is more preferable.

[Blending amount]
Although the compounding quantity Y of the particle group (B) in a granular detergent is not specifically limited, It is preferable to set within the range with which Formula (2) and Formula (3) are satisfy | filled.
The blending amount of the particle group (B) is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more with respect to the total mass of the granular detergent. When the content is 10% by mass or more, the solubility of the granular detergent in water is good. In consideration of the balance with other components, the upper limit of the amount Y is preferably 50% by mass or less, and more preferably 30% by mass or less.

<Optional component>
The granular detergent according to the present invention is a bleaching agent, a bleaching activator, a bleaching activation catalyst, an enzyme, a recontamination preventive agent (carboxymethylcellulose, etc.), an antifoaming agent, as long as the effects of the present invention are not impaired. In addition, components such as a surface coating agent (zeolite, etc.), a fragrance, and a pigment can be contained.
These optional components may be powder-mixed with the particle group (A) and the particle group (B) as a particle group, and by spraying or the like, any one of the particle group (A) and the particle group (B) may be mixed. It may be attached.

Examples of the bleaching agent include sodium percarbonate, sodium perborate, sodium perborate trihydrate, and the like. Among these, sodium percarbonate is preferable.
Although content of the bleaching agent in a granular detergent is not specifically limited, It is preferable that it is 5-20 mass% with respect to the total mass of a granular detergent.
When the content of the bleaching agent is equal to or more than the above lower limit value, better detergency can be easily obtained. When the content of the bleaching agent is not more than the above upper limit, yellowing of the granular detergent can be more easily suppressed.
Moreover, it is preferable that the said bleaching agent is mix | blended with a powder detergent as a particle group containing this.
Although the average particle diameter of the particle group containing a bleaching agent is not specifically limited, From the point of suppression of yellowing of a granular detergent, it is preferable that it is more than the average particle diameter of a particle group (B).

Although it does not specifically limit as said fragrance | flavor, What adheres to the said particle group (B) and is used is mentioned.
Moreover, the said fragrance | flavor may be powder-mixed with particle group (A) and particle group (B) as a particle group containing a fragrance | flavor, and any one of particle group (A) or particle group (B) by spraying etc. You may make it adhere to 1 or more types. From the viewpoint that yellowing of the granular detergent can be further suppressed, it is preferable that the granular detergent is attached to the particle group (B) by spraying.

<Moisture content>
The water content in the granular detergent is preferably 2 to 9% by mass, more preferably 2.5 to 8% by mass, and further preferably 3 to 7% by mass. If the water content is 2% by mass or more, the solubility in water tends to be good, and if it is 9% by mass or less, the fluidity after storage tends to be good.

<Container>
Examples of the container filled with the granular detergent of the present invention include regular containers such as cartons and bottles used for storing granular detergents, and irregular containers such as pillows, gussets, and pouches.
Although it does not specifically limit as a raw material of the said container, Paper, a plastic film, etc. are mentioned. Examples of the plastic film include metal composite plastic films, single-layer or multilayer films of various plastics, and the like.
In recent years, granular detergents have been filled in refill containers such as pouches from the viewpoint of resource saving and the like. Granular detergent filled in an irregular shaped container such as a pouch is easily yellowed by pressure when it is transported or stored in a store, or is held by a person.
The granular detergent of the present invention is excellent in the yellowing suppression effect as described above, and an excellent yellowing suppression effect is obtained even when filled in an irregular container such as a pouch.
For example, a granular detergent filled in an irregular container causes mottled discoloration of the detergent particles present in the wrinkles and dents of the irregular container, but the granular detergent of the present invention also exhibits such mottled discoloration. Easy to suppress.

In the detergent product in which the granular detergent of the present invention is filled in a container, the head space in the container is preferably 30% by volume or less, and more preferably 20% by volume or less.
By making the head space in a container below the said upper limit, yellowing of granular detergent can be suppressed more easily.
The head space in the present invention is obtained by subtracting the capacity of the granular detergent filled in the container from the maximum capacity of the container. The capacity of the granular detergent is determined by the product of the filling mass of the granular detergent and the inverse of the bulk density of the granular detergent.

In addition, the detergent product in which the granular detergent of the present invention is filled in the container has a volume ratio of the particle group (B) in the granular detergent to the head space in the container [volume occupied by the particle group (B) / volume in the container Head space, hereinafter also referred to as “particle group (B) / head space”. ] Is preferably 0.6 to 2.5.
When the particle group (B) / head space is within the above preferable range, yellowing of the granular detergent can be more easily suppressed.
In addition, the volume which particle group (B) occupies in granular detergent is calculated | required by the product of the filling mass of particle group (B), and the reciprocal number of the bulk density of particle group (B).

<Production method of granular detergent>
The granular detergent of the present invention can be easily produced by powder-mixing the particle group (A) and the particle group (B) so as to satisfy the formula (1).
In the granular detergent obtained by powder-mixing these particle groups, the particles (A particles and B particles) of each particle group exist as independent particles.

  As the particle group (A) and the particle group (B), commercially available products may be used, respectively, and those manufactured by a known manufacturing method may be used. The particle group (A) and the particle group (B) can be produced by a production method described later. When using a commercially available product, it may be adjusted to a desired average particle size by sieving as necessary.

As a mixing method of the particle group (A) and the particle group (B), a known powder mixing method can be used. For example, a conventionally known powder mixing apparatus (for example, a horizontal cylindrical rolling mixer or a V-type mixer). ) And the particle group (A) and the particle group (B) are added and mixed.
The order of charging the particle group (A) and the particle group (B) into the powder mixing device is not particularly limited, and the particle group (A) and the particle group (B) are all charged in the mixing device in advance and mixed. Alternatively, the particle group (A) and the particle group (B) may be sequentially added to the mixing apparatus and mixed in any order.
When any other particle group is blended in addition to the particle group (A) and the particle group (B), the other particle group is premixed with either the particle group (A) or the particle group (B). Alternatively, other particle groups together with the particle group (A) and the particle group (B) may be charged in a mixing device in advance and mixed. Moreover, after mixing particle group (A) and particle group (B), you may add and mix by spraying liquid components, such as a fragrance | flavor.
However, from the viewpoint of the solubility of the granular detergent, the amount of water-insoluble component (zeolite, etc.) used is within a range where the content of the water-insoluble component in the granular detergent is less than 10% by mass with respect to the total mass of the granular detergent. It is preferable to be inside.

[Production 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 a conventionally known method.
For example, a spray drying slurry is prepared by dispersing and dissolving a part of the raw material (surfactant, optional component) constituting the particle group (A) in water (slurry preparation step), and the spray drying slurry is spray dried. Dry by a machine to obtain spray-dried particles (spray drying process). Next, the obtained spray-dried particles are granulated together with the remaining raw materials (granulation step). Thereby, a particle group (A) is obtained. Thereafter, the particle group (A) may be sieved as necessary to adjust to a desired average particle size (sieving step).

[Production Method of Particle Group (B)]
The particle group (B) of the single crystal particles of the water-soluble inorganic salt can be produced by a conventionally known method.
For example, since water-soluble inorganic salts are available in various great grades from the market, one that is a group of single crystal particles is selected from these, and if necessary, a desired average particle size is obtained. Sieving.
As a sieving method, for example, a plurality of types of sieves are prepared and stacked in the order of a sieve having a small mesh size to a sieve having a large mesh size to form a sieve unit, and the particle group (B) is placed above the sieve unit. There is a method of charging and sieving the sieve unit. By collecting the particle groups (B) remaining on each sieve for each sieve and mixing the collected particle groups (B), the particle groups (B) having a desired average particle diameter can be obtained.

Moreover, you may attach a fragrance | flavor to the particle group (B) of the single crystal particle | grains of water-soluble inorganic salt as needed.
The perfume can be attached to the particle group (B) by a conventionally known method. For example, the particle group (B) is introduced into a mixer such as a container-rotating cylindrical mixer and the particle group (B). The method of spraying a fragrance | flavor to this while stirring and flowing is mentioned. Under the present circumstances, in order to fix a fragrance | flavor, you may spray coating components, such as a nonionic surfactant, simultaneously with a fragrance | flavor or after spraying a fragrance | flavor.

<How to use granular detergent>
The granular detergent of the present invention can be used for washing laundry.
As a washing method of the washing object using the granular detergent, for example, the washing liquid having a concentration of the granular detergent of 0.02 to 2% by mass is used to wash the washing object in the washing machine, or the washing liquid is washed. Conventionally known cleaning methods, such as a method of soaking, are included.
Examples of the articles to be washed include textiles such as clothing, fabrics, curtains, and sheets.

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
The following materials were used.

[Raw material of particle group (A)]
MES: sodium salt of fatty acid methyl ester sulfonate having 16 carbon atoms in fatty acid residue / 18 carbon atoms in fatty acid residue = 80/20 (mass ratio) (manufactured by Lion Corporation, AI = 70%, remaining is unreacted fatty acid) Methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).
LAS-Na: linear alkyl (10 to 14 carbon atoms) sodium benzenesulfonate (Lypon LH-200 (LAS-H pure content 96% by mass, manufactured by Lion Corporation) 48% by mass hydroxylation when preparing the surfactant Neutralize with aqueous sodium).
-Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure; 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).
Nonionic surfactant: LMAO-90 (trade name, manufactured by Lion Chemical) [polyoxyethylene (EO15 ^* ) alkyl (C12-14 ^* ) ether]. * “EO15” indicates that the average added mole number of ethylene oxide is 15, and (C12-14) indicates that the alkyl group has 12 to 14 carbon atoms.
Sodium carbonate: granular ash, average particle size 320 μm, bulk density 1.07 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Potassium carbonate: potassium carbonate (powder), average particle size 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Sodium sulfate: neutral anhydrous sodium sulfate A0, manufactured by Shikoku Kasei Kogyo Co., Ltd.
MA agent: acrylic acid-maleic anhydride copolymer sodium salt, trade name: Aqualic TL-400, pure 40% by weight aqueous solution, manufactured by Nippon Shokubai Co., Ltd.
Zeolite: A-type zeolite, trade name: Shilton B, pure content 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.
Fluorescent agent: Tinopearl CBS-X (trade name, manufactured by BASF, distyryl biphenyl derivative, water-soluble fluorescent agent) / Tinopearl AMS-GX (trade name, manufactured by BASF, bis (triazinylaminostilbene) disulfonic acid derivative , Quasi-dispersing fluorescent agent) = 1/1.

[Raw material of particle group (B)]
B-1: Sodium hydrogen carbonate single crystal particle group, sodium bicarbonate, BICARTEC 27/50 (trade name, manufactured by SOLVAY CHIMICA ITALIA SPA), average particle diameter of 300 μm, bulk density of 0.96 g / cm ³ . Maximum reflection intensity of 10,000 in X-ray diffraction measurement.
B-2: Sodium hydrogen carbonate single crystal particle group, average particle diameter 170 μm, bulk density 1.00 g / cm ³ . Prepared by sieving b-1. Maximum reflection intensity of 10,000 in X-ray diffraction measurement.
B-3: A group of single crystal particles of sodium hydrogen carbonate, an average particle diameter of 190 μm, and a bulk density of 0.98 g / cm ³ . Prepared by sieving b-1. Maximum reflection intensity of 10,000 in X-ray diffraction measurement.
-Fragrance | flavor: The fragrance | flavor composition C-1 as described in the Example of Unexamined-Japanese-Patent No. 2012-140555.
Nonionic surfactant: LMAO-90.

[Raw material of particle group (B ′)]
The particle group (B ′) is a comparative component of the particle group (B).
B′-1: Sodium hydrogen carbonate particle group (manufactured by Zhejiang Jinke Chemicals), average particle size 300 μm, bulk density 0.96 g / cm ³ . Maximum reflection intensity 1500 in X-ray diffraction measurement.
-Fragrance | flavor: The fragrance | flavor composition C-1 as described in the Example of Unexamined-Japanese-Patent No. 2012-140555.
Nonionic surfactant: LMAO-90.

[Optional ingredients]
Particle group (C-1): sodium percarbonate, manufactured by Zhejiang Jinke Chemicals, trade name “SPCC”. Particles consisting of 89% by weight of sodium percarbonate, 4.5% by weight of sodium carbonate, 4.5% by weight of sodium chloride, and 1% by weight of water are coated with 1% by weight of a coating agent. Average particle diameter 900 μm, bulk density 0.95 g / cm ³ .
Particle group (C-2): sodium percarbonate, average particle diameter 200 μm, bulk density 1.00 g / cm ³ . Prepared by sieving the particle group (C-1).
CMC: Carboxymethylcellulose particles, manufactured by Daicel Corporation, trade name “CMC Daicel 1170”.
Enzyme: Sabinase 12T, manufactured by Novozymes.

<Production of Particle Group (A)>
[Production of Particle Group (A-1)]
In accordance with the composition and production conditions shown in Table 1, the particle group (A-1) was produced by the following steps (1) to (3).

・ Process (1)
A part of nonionic surfactant (25% by mass relative to MES) is added to an aqueous slurry of MES (prepared to a water concentration of 25% by mass), and thin film drying is performed until the water concentration reaches 11% by mass. The mixture was concentrated under reduced pressure by a machine to obtain a mixed concentrate of MES and nonionic surfactant.

・ Process (2)
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 80 ° C. To this, a surfactant excluding MES and nonionic surfactant was added and stirred for 10 minutes. Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the A-type zeolite (from the blending amount shown in Table 1 below, 1.0% by mass for addition at the time of kneading added in the following step (3), and for the grinding aid 5. Sodium carbonate, potassium carbonate and sodium sulfate were added in an amount excluding 0% by mass).
After further stirring for 20 minutes to prepare a slurry for spray drying having a water content of 38% by mass (slurry preparation operation), spray drying was performed using a countercurrent spray drying tower at a hot air temperature of 280 ° C., and the average particle size was 320 μm. Spray dried particles having a bulk density of 0.30 g / cm ³ and a water content of 6% by mass were obtained (spraying operation).

・ Process (3)
The obtained spray-dried particles, the mixed concentrate obtained in step (1), 1.0% by mass of A-type zeolite, nonionic surfactant (the remainder excluding the nonionic surfactant in the mixed concentrate), fluorescence A water and a surfactant containing a surfactant are added to a continuous kneader (KRC-S12 type, manufactured by Kurimoto Seiko Co., Ltd.) and kneaded under conditions of a rotation speed of the kneader of 110 rpm and a jacket temperature of 60 ° C. A mass% kneaded product was obtained (kneading treatment). The kneaded product was cut with a cutter (cutter peripheral speed is 5 m / s) while being extruded with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm, and the length A pellet-shaped molded product of about 5 to 30 mm was obtained.
Next, Fitz arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s) coexisting with an amount equivalent to 5.0% by mass of A-type zeolite as a grinding aid to the obtained pellet-shaped molded product. Crush using a mill (manufactured by Hosokawa Micron Corporation, DKA-3) (screen hole diameter: 1st stage 8mm / 2nd stage 5mm / 3rd stage 3mm, rotation speed: 1st stage 4700rpm / 2nd stage 4700rpm / 3 Stage 4700 rpm), particle group (A-1) was produced (granulation operation).

[Production of Particle Group (A-2) to (A-4)]
A particle group (A-2) was obtained in the same manner as the particle group (A-1) except that the rotation speed of the kneader, the hole diameter of the Fitzmill, and the rotation speed were changed to those shown in Table 1.
Moreover, except having changed the composition of the particle group into what is shown in Table 1, particle group (A-3) and (A-4) were manufactured like the particle group (A-1).

  Table 1 shows the average particle diameter R, the half-value width m of the particle size distribution, and the bulk density a of the obtained particle groups (A-1) to (A-4).

<Production of particle group (B)>
<Production of Particle Group (B-1)>
According to the composition shown in Table 2, the component (b-1) was introduced into a container rotating cylindrical mixer, and the fragrance was sprayed and adhered while rotating the container. At that time, a nonionic surfactant was also sprayed simultaneously to immobilize the fragrance. After completion of the spraying of the fragrance and the nonionic surfactant, the particles were mixed for 5 minutes while rotating the container to produce a particle group (B-1).

<Production of Particle Group (B-2) to (B-3), (B′-1)>
According to the composition shown in Table 2, particle groups (B-2) to (B-3) were produced in the same manner as the particle group (B-1). A particle group (B′-1) was produced in the same manner as the particle group (B-1) except that the component (b′-1) was used instead of the component (b-1).

  Table 2 shows the average particle diameter r, the half-value width n of the particle size distribution, and the bulk density b of the obtained particle groups (B-1) to (B-3) and (B′-1).

[Examples 1 to 12, Comparative Examples 1 to 5]
According to the composition shown in Tables 3 to 5, the particle group (A), the particle group (B) or the particle group (B ′), the particle group (C-1) or the particle group (C-2), and CMC The mixture was simultaneously charged at a rate of 15 kg / min into a container rotating cylindrical mixer and mixed. Thereafter, the enzyme was put into the mixer and mixed for 5 minutes to prepare granular detergents of each example.
Tables 3 to 5 show the compositions (formulation components, content (mass%)) of the obtained granular detergent.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, “r / R”, “X / Y”, “(a × R ³ ) / (b × r ³ ) × 0.3”, “(a × R ³ ) / (b ×” of Comparative Example 5 “r ³ ) × 3.0” and “n / m” are values based on the particle group (B ′) used in place of the particle group (B).

<Method for evaluating granular detergent>
About the granular detergent of each example, the inhibitory property of mottled discoloration and the inhibitory property of a color tone change were evaluated as follows. As described above, the mottled discoloration is a discoloration that occurs in places where pressure is applied to the granular detergent such as the bottom and corners of the carton, wrinkles and recesses of the pouch. On the other hand, the change in color tone is to reduce the granular detergent as shown below and evaluate how much the color tone of the granular detergent before and after storage changes, and evaluate the change in color tone of the granular detergent as a whole. It is.
The evaluation results are shown in Tables 3-5.

[Evaluation of mottled discoloration inhibition]
The granular detergent of each example was filled in the containers (pouches or cartons) shown in Tables 3 to 5 so as to have the headspaces shown in Tables 3 to 5, respectively.
As the pouch, one having a volume of 1200 mL and a three-layer structure (with a pinhole having a diameter of 0.3 mm) of polyethylene / polypropylene / nylon = 130 μm / 25 μm / 15 μm from the outside was used.
As the carton, a bottom surface of 155 mm × 95 mm, a height of 135 mm, and a coated paper made of coated cardboard / polyethylene / coated cardboard from the outside was used.
The container filled with the granular detergent was subjected to vibration (JIS Z0232) that was assumed to be transported by freight car, and then stored in a constant temperature and humidity room for 4 weeks. Meanwhile, the constant temperature and humidity chamber was repeatedly operated at 45 ° C. and humidity 90% RH for 24 hours and at 25 ° C. and humidity 65% RH for 12 hours.
Thereafter, the granular detergent was taken out of the container, and the degree of mottled discoloration was visually observed and evaluated based on the following evaluation criteria. In this evaluation, 1 to 3 points were accepted.
≪Evaluation criteria for mottled discoloration inhibition≫
5: Mottled discoloration occurs remarkably.
4: Mottled discoloration clearly occurs.
3: A level where mottled discoloration slightly occurs but is not a problem.
2: Mottle discoloration hardly occurs.
1: Mottled discoloration cannot be confirmed.

[Evaluation of suppression of color change]
In the above [Evaluation of mottle discoloration inhibition], 770 g of granular detergent after storage for 4 weeks was reduced to 6 g, and a color difference meter (trade name: SE200 type, manufactured by Nippon Denshoku Co., Ltd.) was used. The b value was measured, and the difference between the b values before and after storage (Δb value) was determined by the following formula. A Δb value of 2.0 or less was accepted. The term “reduction” is a particle group dividing method described in JIS K3362, and is an operation for uniformly dividing the particle group.
Δb = (b value of granular detergent after storage) − (b value of granular detergent before storage)

From the results shown in Tables 3 to 5, it was confirmed that the granular detergents of Examples 1 to 12 to which the present invention was applied can suppress mottled discoloration and also can suppress color change before and after storage.
On the other hand, the granular detergent (Comparative Example 5) using the particle group (B ′) instead of the granular detergent (Comparative Examples 1 and 2) and the particle group (B) whose r / R ratio does not satisfy the scope of the present invention is: Mottled yellowing occurred in the granular detergent. Further, the Δb value was large, and the change in color tone before and after storage was large.
The granular detergent filled in the carton (Comparative Examples 3 and 4) had less mottled discoloration and small color change compared to Comparative Examples 1, 2 and 5, but the granular detergent filled in the same carton Compared with (Examples 11 and 12), the mottled discoloration was inferior and the color tone change was also large.
From the above results, it was confirmed that the granular detergent to which the present invention was applied was excellent in the effect of suppressing discoloration such as yellowing.

Claims (4)

A granular detergent comprising a particle group (A) containing a surfactant and a particle group (B) of single crystal particles of a water-soluble inorganic salt, and satisfying the following formula (1) .
0.45 <r / R <1.00 (1)
However, R in Formula (1) is the average particle diameter (μm) of the particle group (A), and r in Formula (1) means the average particle diameter (μm) of the particle group (B). To do.   A detergent product, wherein the granular detergent according to claim 1 is filled in a container.   The detergent product according to claim 2, wherein the container is an amorphous container. It is a manufacturing method of the granular detergent according to claim 1,
A method for producing a granular detergent, comprising a step of powder-mixing the particle group (A) and the particle group (B).