JP2003105400A - Granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granular detergent composition compatible with the suppressions both of classification and solidification. SOLUTION: The granular detergent composition contains at least two kinds of particles in which the total contents excluding the particles of the largest content is 3-50 mass%, and a tensile rupture stress is 3,000-60,000 Pa. The composition is obtained by mixing particles having Z1 of an inclination in Rosin- Rammler plot with another type of particles having a composition and/or production method different from the composition and/or the production method of those particles and having Z2 of an inclination in Rosin-Rammler plot. In the composition, a mode in which the ratio of Z1/Z2 is 1/2 to 2/1, and a mode in which the composition is obtained by mixing particles existing in a region surrounded with straight lines of y=0.5417x+0.172, y=0.7643x-0.815, x=1.50 and x=2.05 wherein x is a true density of the group of the particles, and y is a bulk density of the group of the particles, are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a method for producing two or more kinds of particles.
Granular detergent composition containing, both classification and suppression of solidification
(Mainly for clothing and dishwashers). [0002] 2. Description of the Related Art Conventionally, granules represented by compact detergents
In detergents, the particle diameter of the constituent particles is not uniform,
Also, for better handling for producers and consumers
In addition, the fluidity is relatively good. Because of this, granular
Detergents are transported through manufacturing processes and into consumer hands.
Classification is always generated depending on the process or the carrying of the consumer.
The situation is easy. Furthermore, in order to improve the function of granular detergent,
3% by mass or more of other foreign particles other than the main granular detergent
When blending, particle size distribution and particle size
Since the surface condition is probably different, further classification is
Easy to play. Therefore, it is possible to improve the classification problem.
Various attempts have been disclosed. For example, Japanese Patent Application Laid-Open No. 2001-3088,
2001-3094, JP-A-2001-131599
In each of the publications, detergent particles having a specific dissolution rate and
And enzyme-containing particles by mixing
There is disclosed a method for preventing classification. Also, JP 20
No. 00-256696, each describes a specific funnel flow.
Mixing detergent particles with water resistance and bulk density with bleach activator
To prevent classification of bleach activators by doing
Is disclosed. However, in order to prevent the classification, the flow is simply measured.
Deterioration of mobility can cause the granular detergent to solidify during storage
Problem arises. Therefore, such granular washing
Many attempts to prevent solidification of the agent have also been disclosed. example
For example, Japanese Unexamined Patent Application Publication No. 2001-3082 discloses a specific structure.
By surface modifier containing crystalline alkali metal silicate,
A method for coating the surface of detergent particles is disclosed. or,
JP 2001-11499 A discloses that a surfactant, water
Contains poorly soluble inorganics and carbonates, average particle size of 150 to
High bulk density detergent with a bulk density of 500 g / L or more, 500 μm
A particle group having a particle diameter of 710 μm or more;
Particles having a particle size of less than 25 μm are each a total of the detergent particles.
10% by mass or less and hardly soluble in water in the detergent particles.
The sum of the content of the inorganic mineral and the carbonate is 10 to 70% by mass,
The mass ratio of the inorganic substance to the carbonate is 1/2 or more,
By obtaining a group of high bulk density detergent particles that is less than 1,
A method that ensures solubility, cleanability, and prevents solidification
Is disclosed. Further, JP-A-2000-351998
In the publication, the average particle size is 150 to 500 μm, and the particle size distribution is
The value obtained by dividing the standard deviation of
10 seconds or less, preferably 95% dissolution time 60 to 2
Fill the specific container with the high bulk density granular detergent composition of 00 seconds
To ensure solubility and prevent solidification
A method is disclosed. However, these methods
All have conflicting properties such as classification and solidification.
Sometimes there was a problem instead of suppressing it. [0005] SUMMARY OF THE INVENTION The present invention
Tasks to solve the problems in
The title. That is, according to the present invention, both classification and suppression of solidification are performed.
It is intended to provide a compatible granular detergent composition
You. [0006] [MEANS FOR SOLVING THE PROBLEMS]
The means are as follows. That is, <1> Contains at least two or more types of particles, and
And the total amount of particles excluding the type of particles with the highest content
The weight is 3 to 50% by mass and the tensile rupture stress is 30
A granular detergent having a pressure of from 00 to 60000 Pa
Composition. In the present invention, the following embodiments are preferred.
New <2> The slope in the rosin Lambra plot is Z1.
Particles differ in composition and / or manufacturing method from the particles,
Particles having a slope of Z2 in the rosin Lambra plot
It is obtained by mixing, and the Z1 / Z2 ratio is 1/2 to 2/1.
The granular detergent composition according to <1>. <3> x is the true density of the particle, and y is the bulk density of the particle group.
Then, a straight line y = 0.5417x + 0.172, y =
0.7643x-0.815, x = 1.50 and x
= 2.05 obtained by mixing particles in the range surrounded by
The granular detergent composition according to the above <1> or <2>,
You. [0008] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The granular detergent composition of the present invention comprises at least two kinds of particles.
And the particles of the type with the highest content in the particles
The total content of particles except for 3 to 50% by mass,
The tensile rupture stress is 3000 to 60000 Pa. Said
In the granular detergent composition, the kind of the most content
3-40% by mass as the total content of the particles excluding the particles
Is preferably, and more preferably 3 to 30% by mass. Containing
If the amount exceeds the above numerical range, classification or solidification occurs
I will. <Tensile rupture stress and the like in granular detergent composition
Various physical properties of the granular detergent composition of the present invention
Two or more kinds of detergent particles and particles of various function improvers
To prevent simultaneous classification and solidification of
Force must be within a certain numerical range. The surface adhesion
Is the tensile rupture stress measured by the measurement method described below.
It is represented by [Pa]. [0010] The surface adhesion amount is within the specific numerical range.
Therefore, the tensile breaking stress is 3000 to 6
Must be 0000 Pa, 10,000-4000
It is preferably 0 Pa. The tensile rupture stress is 30
If the pressure is less than 00 Pa, the flow of the detergent particles or the detergent particle mixture
The mobility is too high and it is easy to classify.
If it exceeds, the surface adhesion is too large and it is easy to solidify. << Method of Measuring Tensile Rupture Stress >> Hosokawa
Using an AG robot manufactured by Micron Co., Ltd.
Possible metal cell (cell inner diameter 25 mm x height 37
mm), the mixture is filled with 15 g,
Compression force 980N (maximum compression pressure 2.0MPa), when holding
0 seconds, compression speed 1.0mm / sec,
Tension spring wire diameter 1.2mm, tension speed 0.4mm / sec
c, pull only the upper cell under the condition of 20 ° C.
The maximum tensile stress when breaking up and down is defined as the tensile breaking stress.
You. The granular detergent composition of the present invention includes
Simultaneous suppression of classification and solidification of two or more types of particles
At a higher point, the slope in the rosin Lambra plot is
The particles having the composition "Z1"
Are different, and the slope in the rosin Lambra plot is
It is obtained by mixing different particles of “Z2”.
Therefore, it is preferable that the "Z1 / Z2" ratio is 1/2 to 2/1.
New Note that the rosin Lambra plot is a
Usually used when the particle size distribution is relatively wide, such as for grinding products.
If the particle size distribution is approximated according to the rosin
This is the plotting method. For example, open your eyes on a saucer
Laminating various sieves from the bottom in order of decreasing size
When classifying, etc., the opening of each sieve is X, and
Let Y be the integrated mass frequency% on the sieve of the particles on the sieve, lo
plot log.log (100 / Y) against gX
The slope of the least-squares approximation line at this time is Z. Z is equal
The particle size distribution is wider as the value of Z is smaller. Departure
In the case of mixing two types of particles,
Z of the particle is defined as "Z1" and Z of the other particle is defined as "Z2"
However, when mixing three or more types of particles,
Z of most kinds of particles is “Z1”, and Z of other particles is
The Z of the mixture can be measured as “Z2”. The "Z1 / Z2 ratio" is 1/1.
8 to 1.8 / 1 is more preferable, and 1 / 1.4 to 1.4 /
1 is more preferred. The “Z1 / Z2 ratio” is not 1/2
If it is full or more than 2/1, the particle size
Classification may be accelerated by unevenness of the cloth. In addition,
As a sieve used when performing rosin Lambra plots in the light
Is JISZ 8801-1: 2000 "Testing sieve part 1: metal mesh
The sieve described in "Sieve" can be suitably used. [0015] In the granular detergent composition of the present invention,
Higher effect of simultaneously classifying and solidifying various particles
The true density of various particles is x, and the bulk density of the particles is y.
Then, a straight line y = 0.5417x + 0.172, y =
0.7643x-0.815, x = 1.50 and x
= 2.05 obtained by mixing particles in the range surrounded by
It is particularly preferred that The particles obtained by mixing particles outside the above range are obtained.
Storage and transportation due to the specific gravity difference between each mixed particle
Classification of time may be promoted. <Constitution of Granular Detergent Composition>
The detergent composition comprises at least two or more types of particles.
Particles excluding the particles with the highest content in the particles
Is 3 to 50% by mass. The granular detergent composition
As, for example, different production methods and / or compositions
An embodiment comprising two or more detergent particles, one or more detergent particles,
And one or more types of particles other than detergent particles such as function enhancer particles.
And the like including other particles. [Detergent Particles] The detergent particles include a surfactant.
Other components, including compounds and builders as needed
including. -Surfactant compound- As the surfactant compound, an anionic surfactant,
Nonionic surfactant, cationic surfactant, and amphoteric
Surfactants. -Anionic surfactant- As the anionic surfactant, conventionally, in detergents
There is no particular limitation as long as it is used.
Various known anionic surfactants are included. For example,
The following anionic surfactants shown in (1) to (12) are mentioned.
Can be (1) having an alkyl group having 8 to 18 carbon atoms
Linear or branched alkylbenzene sulfonate (L
AS or ABS). (2) An alkane sulfonate having 10 to 20 carbon atoms. (3) α-olefin sulfonate having 10 to 20 carbon atoms
(AOS). (4) Alkyl sulfate or alkenyl having 10 to 20 carbon atoms
Sulphate (AS). (5) A linear or branched alkyl group having 10 to 20 carbon atoms
Or having an alkenyl group, on average 0.5-10 mol
Ethylene oxide, propylene oxide, butylene
Oxide and ethylene oxide and propylene
Oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.9.
Alkyl ether to which at least one of 1) is added
Sulphate or alkenyl ether sulphate (AE
S). (6) Straight or branched chain having 10 to 20 carbon atoms
Is an alkylphenyl or alkenylphenyl group
Having an average of 3 to 30 moles of ethylene oxide and propylene.
Len oxide, butylene oxide, and ethylene
Oxide and propylene oxide (molar ratio: 0.1
/9.9 to 9.9 / 0.1)
Alkyl phenyl ether sulfate or Al
Kenyl phenyl ether sulfate. (7) A linear or branched alkyl group having 10 to 20 carbon atoms
Or having an alkenyl group, on average 0.5-10 mol
Ethylene oxide, propylene oxide, butylene
Oxide and ethylene oxide and propylene
Oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.9.
Alkyl ether to which at least one of 1) is added
Carboxylate or alkenyl ether carboxylate. (8) Alkyl glycer having 10 to 20 carbon atoms
Alkyl polyhydric alcohols such as
-Sulfate. (9) Saturated or unsaturated α-sulfo fat having 8 to 20 carbon atoms
Acid salt or its methyl ester, ethyl ester, or
Is a propyl ester (α-SF or MES). (10) Long-chain monoalkyl phosphate, dialkyl phosphoric acid
Salt or sesquialkyl phosphate. (11) polyoxyethylene monoalkyl phosphate,
Lioxyethylene dialkyl phosphate or polyoxy
Siethylene sesquialkyl phosphate. (12) Higher fatty acid salts having 10 to 20 carbon atoms. The anionic surfactant is sodium,
Alkali metal salts such as potassium, amine salts, ammonium
It may be used as a salt or the like. The anionic surfactant
May be used alone or in combination of two or more.
Good. Among the anionic surfactants, for example, linear
Alkali metal of alkylbenzene sulfonic acid (LAS)
Salt (eg, sodium or potassium salt), AO
Alkali metal salts of S, α-SF and AES (for example,
Lium or potassium salts), alkali metals of higher fatty acids
Salts (eg, sodium or potassium salts) are preferred
No. --Nonionic surfactant-- As the nonionic surfactant, conventionally, in detergents
There is no particular limitation as long as it is used.
There are various known nonionic surfactants. For example,
Nonionic surfactants shown in (1) to (11) below are listed.
Can be (1) C6 to C22 (preferably carbon
The aliphatic alcohols of formulas 8 to 18) are
The alkylene oxide is used in an amount of 3 to 30 mol on average (preferably,
5 to 20 mol) added polyoxyalkylene alkyl
(Or alkenyl) ether. Among these, polio
Xylene ethylene (or alkenyl) ether,
Lioxyethylene polyoxypropylene alkyl (or
Alkenyl) ethers and the like are preferred. Used here
As aliphatic alcohols, primary alcohols and secondary alcohols
And primary alcohols are preferred.
No. Further, the alkyl group may have a branched chain.
No. (2) Polyoxyethylene alkyl (or
Alkenyl) phenyl ether or long-chain fatty acid alkyl
Alkylene oxide between the ester bonds of the kill ester
A fatty acid alkyne represented by the following general formula (I)
Ester alkoxylate. General formula (I) R¹CO (OA)_nOR² In the general formula (I), R¹CO has 6 to 22 carbon atoms.
(Preferably 8 to 18) fatty acid residues. OA is
2 to 2 carbon atoms such as ethylene oxide and propylene oxide
4 (preferably 2 to 3) alkylene oxide addition units
Represents the position. n is the average number of moles of alkylene oxide added
And generally 3 to 30 (preferably a number of 5 to 20)
is there. R²Is low which may have a substituent having 1 to 3 carbon atoms.
Represents a lower alkyl group. [0029] (3) Polyoxyethylene sorbitan fatty acid esters. (4) Polyoxyethylene sorbite fatty acid ester. (5) Polyoxyethylene fatty acid esters. (6) Polyoxyethylene hydrogenated castor oil. (7) Glycerin fatty acid ester. (8) fatty acid alkanolamides. (9) Polyoxyethylene alkylamine. (10) Alkyl glycosides. (11) Alkylamine oxide. Among the nonionic surfactants, the melting point is
Polyoxyethylene alcohol having an HLB of 9 to 16 at 40 ° C or lower
Alkyl (or alkenyl) ether, polyoxyethylene
Polyoxypropylene alkyl (or alkenyl)
Ethylene oxide in ether and fatty acid methyl ester
Added fatty acid methyl ester ethoxylate, fatty acid
Ethylene oxide and propyleneoxy to methyl ester
Fatty acid methyl ester ethoxypropoxy
The rate is preferred. These nonionic surfactants
One type may be used alone, or two or more types may be used in combination.
No. --Cationic surfactant-- As the cationic surfactant, conventionally, in detergents
There is no particular limitation as long as it is used.
There are various known cationic surfactants. For example,
Nonionic surfactants shown in the following (1) to (4) are listed.
Can be (1) Di-long chain a represented by the general formula (II)
Lucildi short chain alkyl type quaternary ammonium salt. General formula (II) [0033] Embedded image In the general formula (II), R¹And R
²Has usually 12 to 26 carbon atoms (preferably 14 to 1
8) represents an alkyl group. R³And R⁴Is usually the carbon number
Is an alkyl group of 1-4 (preferably 1-2), benzyl
Group, usually having 2 to 4 (preferably 2 to 3) carbon atoms
Xylalkyl group or polyoxyalkylene group
It represents this. X is halogen, CH₃SO₄, C₂H₅
SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂
And CH₃-C₆H₄-SO₃Represents any of The above-mentioned di long chain alkyl di short chain alkyl type quaternary
As the ammonium salt, specifically, distearyl di
Methyl ammonium salt, dihydrogenated tallow alkyl dimethyla
Ammonium salt, dihydrogenated beef tallow alkylbenzene methylan
Monium salt, distearylmethylbenzylammonium
Salt, distearyl methyl hydroxyethyl ammonium
Salt, distearylmethylhydroxypropylammonium
Salt, distearyl dihydroxyethyl ammonium
Salt, dioleyl dimethyl ammonium salt, coconut
Alkyl dimethyl ammonium salts and the like. or,
Specific examples of the halogen represented by X include a chlorine atom, bromine
Atoms and the like. (2) Mono-length represented by the general formula (III)
Chain alkyl tri-short chain alkyl type quaternary ammonium salt. General formula (III) [0037] Embedded image In the general formula (III), R¹Is
Usually, an alcohol having 12 to 26 (preferably 14 to 18) carbon atoms
Represents a alkyl group. R², R³And R⁴Is usually the number of carbon atoms
Is an alkyl group of 1-4 (preferably 1-2), benzyl
Group, usually having 2 to 4 (preferably 2 to 3) carbon atoms
Xylalkyl group or polyoxyalkylene group
It represents this. X is halogen, CH₃SO₄, C₂H₅
SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂
And CH₃-C₆H₄-SO₃Represents any of ) The above-mentioned mono long chain alkyl tri short chain alkyl type
As the quaternary ammonium salt, for example, lauryl trime
Tylammonium salt, stearyltrimethylammonium
Um salt, hydrogenated tallow alkyltrimethylammonium salt,
Hydrogenated beef tallow alkylbenzene dimethyl ammonium salt,
Tearyl dimethyl benzyl ammonium salt, stearyl
Dimethyl hydroxyethyl ammonium salt, stearyl
Dimethyl hydroxypropyl ammonium salt, steari
Rutrihydroxyethylammonium salt, oleyltri
Methyl ammonium salt, coconut alkyl trimethyl
Ammonium salts and the like. Also, halo represented by X
Examples of the gen include a chlorine atom and a bromine atom. (3) Tetra short represented by the general formula (IV)
Chain alkyl type quaternary ammonium salts. General formula (IV) [0041] Embedded image In the general formula (IV), R¹~ R⁴
Is usually an alkyl having 1 to 4 (preferably 1 to 3)
A kill group or a benzyl group, usually having 2 to 4 carbon atoms (preferably
Is a hydroxyalkyl group of 2-3) and polyoxy
Represents any of alkylene groups. X is a halogen element,
CH₃SO₄, C₂H₅SO₄, 1 / 2SO₄, OH,
HSO₄, CH₃CO₂, And CH₃-C₆H₄-S
O₃Represents any of The above tetra short chain alkyl type quaternary ammonium
For example, tetramethylammonium chloride
Ride, tetraethylammonium chloride, tetra
Butyl ammonium bromide, tetrabutyl ammonium
Tetrabutylammonium hydroxide
Gensulfate, benzyltrimethylammonium
Chloride, benzyltrimethylammonium hydroxy
Side, benzyltriethylammonium chloride,
Benzyl tributyl ammonium bromide, benzyl
Tributyl ammonium chloride, trimethyl phenyl
Ruammonium chloride and the like. (4) Tri long chain a represented by the general formula (V)
Alkyl mono short chain alkyl type quaternary ammonium salt General formula (V) [0045] Embedded imageIn the general formula (V), R¹~ R³Is
Al having 12 to 26 (preferably 14 to 18) carbon atoms
Represents a kill group. R⁴Has usually 1 to 4 carbon atoms (preferably
Is an alkyl group or benzyl group of 1-2), usually having 2 carbon atoms.
-4 (preferably 2-3) hydroxyalkyl groups, and
And any of polyoxyalkylene groups. X is
Halogen element, CH₃SO₄, C₂H₅SO₄, 1/2
SO₄, OH, HSO ₄, CH₃CO₂And CH₃-C
₆H₄-SO₃Represents The above tri long chain alkyl mono short chain alkyl type
As quaternary ammonium salts, for example, trilaurylme
Tylammonium chloride, tristearyl methyl alcohol
Nmonium chloride trioleyl methyl ammonium
Chloride, tricoconut alkyl methyl ammonium
Muchloride and the like. --- Amphoteric surfactant-- As the amphoteric surfactant, conventionally used in detergents
Is not particularly limited as long as the
Various amphoteric surfactants are included. For example,
The amphoteric surfactants shown in (1) to (3) are mentioned. (1) Betaines. For example, lauric acid
Midopropyl betaine, amide ethyl stearate beta
In, carbobetaine, sulfobetaine, etc.
You. (2) imidazoline derivatives. For example, 2-alkyl-
N-carboxymethyl-N-hydroxyethylimidazo
Linium betaine, N-coconut fatty acid acyl-N-cal
Boxyethyl-N-hydroxyethylethylenediamine
Sodium and the like. (3) Phosphate type phosphate type. For example, lecithin (phos
Fatidylcholine and the like. These amphoteric surfactants may be used alone.
Alternatively, two or more kinds may be used in combination. --- Surfactant content-- Content of the surfactant compound in the detergent particles
In order to provide sufficient cleaning performance,
90 mass% is preferred, and 20 to 70 mass% is more preferred.
No. -Builder- As the builder, an inorganic builder and an organic builder
And the like. --- Inorganic builder-- Examples of the inorganic builder include sodium carbonate,
Potassium carbonate, sodium bicarbonate, sodium sulfite,
Sodium sesquicarbonate, sodium silicate, crystalline layered silica
Alkalis such as sodium silicate and amorphous layered sodium silicate
Neutral salts, neutral salts such as sodium sulfate, orthophosphate,
Pyrophosphate, tripolyphosphate, metaphosphate, hex
Phosphates such as sametaphosphate and phytate, the following general
A crystalline aluminosilicate represented by the formula (VI),
Amorphous aluminosilicate represented by formula (VII):
The amorphous aluminosilicate represented by the general formula (VIII)
No. General formula (VI): x1 (M₂O) · Al₂
O₂・ Y1 (SiO₂) ・ W1 (H₂O) In the general formula (VI), M represents sodium, potassium, or the like.
Represents an alkali metal atom of x1, y1 and w1 are each
Represents the number of moles of the component, and generally, x1 is 0.7-1.
Any number of 5, y1 is any number of 0.8 to 6, w
1 represents any positive number. General formula (VII): x2 (M₂O) · Al
₂O₃・ Y2 (SiO₂) ・ W2 (H ₂O) In the general formula (VII), M is sodium, potassium
And the like. x2, y2 and w2 are:
It represents the number of moles of each component, and generally, x2 is 0.7 to
Any number of 1.2, y2 is any of 1.6 to 2.8
The number, w2, represents 0 or any positive number. General formula (VIII): x3 (M₂O) ・ A
l₂O₃・ Y3 (SiO₂) ・ Z3 (P₂0₅) ・ W3
(H₂O) In the general formula (VIII), M is sodium, potassium
Represents an alkali metal atom such as x3, y3, Z3 and
w3 represents the number of moles of each component, and generally, x3 is
Any number of 0.2 to 1.1, y3 is 0.2 to 4.0
And z3 is any of 0.001 to 0.8
And w3 represents 0 or any positive number. Among the inorganic builders, sodium carbonate
, Potassium carbonate, sodium silicate, sodium tripolyphosphate
Thorium and sodium aluminosilicate are preferred
No. These inorganic builders may be used alone.
Alternatively, two or more kinds may be used in combination. -Organic builder- Examples of the organic builder include nitrilotriacetic acid
Salt, ethylenediaminetetraacetate, β-alanine divinegar
Acid salt, aspartic acid diacetate, methyl glycine diacetic acid
Aminocarboxylates such as salts and iminodisuccinates;
Diacetate, hydroxyiminodisuccinate, hydroxy
Siethylethylenediamine triacetate, dihydroxyethyl
Hydroxyaminocarboxylates such as luglycine salts;
Roxy acetate, tartrate, citrate, gluconate, etc.
Hydroxycarboxylate; pyromellitic acid salt, benzoic acid
Polycarboxylate, cyclopentanetetracarboxylate
Cyclocarboxylates such as carboxymethyl tartrone
Carboxymethyloxysuccinate, oxydi
Succinate, tartaric acid mono- or disuccinate, etc.
-Tercarboxylate; polyacrylic acid, acrylic acid-a
Ryl alcohol copolymer, acrylic acid-maleic acid copolymer
Combination, hydroxyacrylic acid polymer, polysaccharide-acryl
Acrylic acid polymers and copolymers such as acid copolymers;
Acid, itaconic acid, fumaric acid, tetramethylene 1,2-
Polymers such as dicarboxylic acid, succinic acid and aspartic acid
Or copolymers; starch, cellulose, amylose, pea
Polysaccharide oxides such as Kuching and carboxymethylcellulose
Polysaccharides such as polyethylene glycol, polyvinyl alcohol
Non-dissociated polymer compounds such as coal and polyvinylpyrrolidone
And the like. Among these organic builders, citric acid
Salts, aminocarboxylates, polyacrylates, and
Crylic acid-maleic acid copolymers are preferred. these
Organic builder may be used alone or in combination of two or more.
The above may be used in combination. --- Content of builder-- In the detergent particles, as the content of the builder
Is 10 to 90 mass% in order to impart sufficient detergency.
%, More preferably 20 to 70% by mass. -Other components- Other components that can be contained in the detergent particles include performance
-Various additives and the like for improving functions are included. example
For example, Disodium4,4'-bis (2-sulf
ostyryl) -biphenyl, Disodiu
m4,4'-bis [(4-anilino-6-mo
rphorino-1,3,5-triazine-2
-Yl) amino] stillene-2,2'-d
optical brighteners such as isulfonate; protease;
Enzymes such as lipase, amylase and cellulase;
Bleaching base such as perboric acid;
Alkanoyl oxybenzene that can improve bleaching performance with
Sulfonic acid and its salts, alkanoyloxybenzene
Carboxylic acid and its salt, tetraacetylethylene diamine
Bleaching activators such as perfume, etc .;
Include dyes and pigments for coloring the whole. Said that
Other components may be used alone or in combination of two or more.
May be used. In addition, the other components are the surfactant
Uniformly mix and granulate with detergent and builder into detergent particles
May be present, or as described below,
, Independently of the detergent particles, in the granular detergent composition
May be contained. -Method for producing detergent particles- As a method for producing the detergent particles, for example, the following method
And the like. Raw material powder and vine for detergent ingredients
After kneading and kneading the dough ingredients, press to extrude and granulate
After the granulation method, kneading and kneading, the resulting solid detergent
Kneading and crushing granulation method, crushing and granulating, binding to raw material powder
Granulation with the addition of powder components and agitation with stirring blades
Method and the binder component is injected while rolling the raw material powder.
A tumbling granulation method in which granulation is performed by atomization is exemplified. As the raw material powder, a surfactant powder
May be used in combination with
If necessary, add water to some or all of the detergent
Prepare a rally, spray dry according to the usual method, dry powder
May be used. As the binder component, 0 to 1
At 00 ° C., a liquid detergent raw material can be used,
For example, water, a surfactant, a water-soluble polymer and the like are preferably mentioned.
Can be --- Extrusion granulation method-- In the extrusion granulation method, kneading and extrusion of any type
Can be used, any type of kneader and press
You may use it in combination with a dispenser. Kneading and extrusion
As a machine, for example, Extrude O Mix
(Manufactured by Hosokawa Micron Corp.) Twin screw kneading extruder
(Manufactured by Kurimoto Iron Works). As a kneading machine
Is a KRC kneader (manufactured by Kurimoto Iron Works), a universal mixing stirrer.
Stirrer (Dalton Co., Ltd.), Nautamixer (Hosokawami)
Clon Co., Ltd.). As an extruder
Is Twin Dome Gran (made by Fuji Paudal Co., Ltd.),
Pellettor Double (Fuji Paudal Co., Ltd.), Fine
・ Luizer (made by Fuji Paudal Co., Ltd.)
You. --- Kneading and crushing granulation method-- In the kneading / crushing granulation method, any type of kneading machine
Combination of crushers, optionally kneading of any type
Machine, extruder and crusher in combination
Can be. As the kneader, a KRC kneader is used.
(Made by Kurimoto Iron Works Ltd.), continuous kneader (Fuji Powder)
Le Co., Ltd.), continuous kneader (Powrex Co., Ltd.)
Universal Mixing Stirrer (Dalton Co., Ltd.), Nauta
-Mixer (manufactured by Hosokawa Micron Corp.)
It is. The kneaded material obtained by these kneaders is used as it is.
It may be crushed, but it is extruded to make it easier to crush.
Pulverizing efficiency is improved by pelletizing with a machine.
I can do it. As the extruder, a pelleter dub is used.
(Fuji Paudal Co., Ltd.), Twin Dome Gran
(Made by Fuji Paudal Co., Ltd.)
Nipaudal Co., Ltd.). Kneading and pressing
As an extruder for simultaneous kneading,
Doomics (manufactured by Hosokawa Micron Corporation), 2 axes
Kneading extruder (manufactured by Kurimoto Iron Works Co., Ltd.) and the like. As a pulverizer for pulverizing the kneaded material, a classifier is used.
Models with clean and rotating blades are preferred. The
Fitzmill (Hosokawa Micron Corporation)
), New Speed Mill (Okada Seiko Co., Ltd.),
Cominator (Fuji Paudal Co., Ltd.), Feather
Mill (manufactured by Hosokawa Micron Corporation) and the like.
In the case of pulverization, by using a grinding aid,
Can be crushed. As the grinding aid, for example,
Inorganic with average particle size (mass average particle size on sieve) of 30 μm or less
Powders are preferred, for example, type A zeolite, fine carbonic acid
Na, white carbon and the like. Of the grinding aid
The amount used is 0.1 to 100 parts by mass of the component to be ground.
5 to 15 parts by mass is preferable, and 2 to 10 parts by mass is more preferable.
New Granulate inorganic powder with a primary particle size of 30 μm or less.
Alternatively, particles having good fluidity may be used. Furthermore, powder
It is also possible to pulverize while cooling by flowing cold air through the crusher. Cold wind
And pulverize the product with a cyclone.
It is also possible to classify the fines. In the pulverization,
Multi-stage pulverization sharpens the particle size distribution
Can be Circumferential speed at the crusher blade
Is preferably 15 to 90 m / s. 15m / s or less
If it is below, the capacity may decrease and productivity may decrease
On the other hand, if it exceeds 90 m / s, it may be easily over-crushed.
You. The tip peripheral speed is preferably 20 to 80 m / s.
And 25 to 70 m / s is particularly preferable. According to the kneading / crushing granulation method, detergent particles
No particle size distribution such as a sieve
It can be manufactured with high productivity. However, the particle size distribution is
In order to make it into a loop, the crushed product is classified using a sieve and used.
You can also. This pulverized product is coated with fine particles.
Or blended with ingredients such as fragrances and enzymes.
You may spray on surfactant etc. --- Agitated granulation method-- In the stirring granulation method, any type of stirring granulator is used.
can do. Among them, stirring with stirring blades
With a shaft at the center of the inside, stirring when the stirring blades rotate
Agitation of a structure that forms a clearance between the blade and the vessel wall
Granulators are particularly preferred. As its average clearance
Is preferably 1 to 30 mm, more preferably 3 to 10 mm.
New If the average clearance is less than 1 mm,
While the mixer may be easily overpowered due to deposition,
If it exceeds 30 mm, the efficiency of consolidation decreases, so the particle size
The distribution can be broad. Long granulation time
It is not preferable because productivity is lowered. Such a structure
As a stirring granulator having a granulation, for example, Henschel Mi
Kisa [Mitsui Miike Kakoki Co., Ltd.], High Speed Miki
Sir [Fukae Kogyo Co., Ltd.], Vertical Granulator
-[Powrex Co., Ltd.] and other devices
The mixing tank has a stirring shaft at the center of the cylinder.
A mixer of the type that mixes powder by attaching
New For example, Ladyge mixer [Matsubo Corporation
Products), Blowshare mixers (produced by Taiheiyo Kiko Co., Ltd.), etc.
No. Preferred granulation conditions in the stirring granulation method are as follows.
It is shown below. (1) Fluid number (Fr number) In the stirring granulation method, a fluid defined by the following formula
Is preferably from 1 to 4, more preferably from 1.2 to 3.
Good. If the Froude number is less than 1, consolidation will occur.
While it may not be promoted, the particle size distribution exceeds 4
May be wider. Formula: Fr (Froude number) = V / (R × g)^0.5 V: Peripheral speed at the tip of the stirring blade [m / s] R: radius of rotation of the stirring blade [m] g: Gravitational acceleration [m / s2] (2) Chopper rotation speed In the stirring granulation method, the stirring granulator used includes:
High-speed rotation to promote the compaction of granulated material and the disintegration of coarse powder
Equipped with a chopper that turns. Times of the chopper
As the rolling speed, the chopper tip speed (peripheral speed) is 20 to
30 m / s is preferred, and 22 to 28 m / s is more preferred.
No. (3) Granulation time, average residence time In the stirring granulation method, the number of times for obtaining a suitable granulated product is increased.
For granulation time in grammatical granulation and continuous granulation
The average residence time is preferably 0.5 to 20 minutes
And 3 to 10 minutes is more preferable. Granulation time and average
If the residence time is less than 0.5 minutes, the time is too short,
Difficulty controlling granulation to obtain suitable average particle size and bulk density
And the particle size distribution may be broad,
If the time exceeds 0 minutes, the time will be too long and the productivity will decrease.
There is. (4) Detergent raw material filling rate In the stirring granulation method, the filling rate of the detergent raw material into the granulator
70% by volume of the total internal volume of the mixer
The following is preferable, and 15 to 40% by volume is more preferable. Previous
If the filling rate (prepared amount) exceeds 70% by volume, mixing
Mixing efficiency of detergent raw materials in the machine is reduced, and granulation can be performed properly.
There may not be. (5) Temperature As a granulator used in the stirring granulation method, a jacket is used.
Provided structures are preferred. Temperature of medium passing through jacket
The degree is preferably 5 to 40 ° C, more preferably 10 to 20 ° C.
Is more preferable. By setting the temperature within this range, a suitable structure can be obtained.
Granulation time for obtaining granules is shortened, and productivity is improved
And the particle size distribution becomes sharp. Also, among the detergent ingredients,
The temperature at which the powder material is at room temperature and the temperature at which the nonionic activator is molten
The temperature inside the mixer needs to be particularly controlled.
There is no. The temperature of the granulated product is the temperature of the raw material,
It is usually 30 to 60 ° C. depending on the conditions. (6) Additive Vine as an additive to promote granulation during granulation
May be added. As the binder, for example,
For example, carboxymethylcellulose, polyethylene glyco
, Polycarboxylates such as sodium polyacrylate, etc.
Water-soluble polymer solution of polyoxyethylene alkyl ether
-Tel, fatty acid monoethanolamide, fatty acid diethanol
Nonionic substances such as amides, fatty acids, sodium silicate water
Solution, water and the like. As the amount of the binder
Is 0.1 to 10 parts by mass of the mixture or the granulated product.
A mass part is preferred, and 0.5-5 mass parts is more preferred. --- Rolling granulation method-- In the tumbling granulation method, granulation is performed by the following method and apparatus.
Is preferred. (1) Batch method The method of charging the compounding ingredients into the granulator is particularly limited.
Not something. When using a batch system, for example, the following ~
Various methods such as can be taken.   First, a builder of organic or inorganic powder,
One or two selected from spray-dried particles and other powder components
After adding more than one kind of particles, liquid composition such as surfactant and water
Add and mix.   Organic or inorganic powder builders, spray-dried particles and
Premix two or more particles selected from other powder components
After charging into a granulator, a liquid such as a surfactant or water
Add and mix body components. Builder of organic or inorganic powder, spraying
One or two selected from dry particles and other powder components
The above particles and a liquid component such as a surfactant and water are granulated.
Charge the machine little by little.   Organic or inorganic powder builders, spray-dried particles and
One or more particles selected from other powder components
After charging a part to the granulator, the remaining organic or inorganic
Selected from builders, spray-dried particles and other powder components
One or more particles and a liquid such as a surfactant or water
The ingredients are charged into a granulator little by little. Builder of organic or inorganic powder, spraying
One or two selected from dry particles and other powder components
Premix the above particles and liquid components such as surfactant and water
This is charged to a granulator. In these methods, first, an organic or inorganic
Choose from powder builders, spray-dried particles and other powder components
One or two or more types that were removed were charged to the granulator.
Then, add a surfactant or water and mix.
Method) is particularly preferred. (2) Continuous method In the case of a continuous method, the detergent raw materials are first mixed continuously.
However, the method of supplying the detergent raw material is not particularly limited.
No. For example, it is possible to take various methods such as
it can. The components of the detergent raw materials are each independently
Supply continuously. Powder materials are mixed beforehand in detergent materials.
And the liquid components such as surfactants and water
To supply.   Mix two or more powder materials in advance among detergent materials
And the remaining powdered raw materials, and liquid components such as surfactants and water.
Minute and continuously.   For liquid components such as surfactants and water and other powder raw materials
Everything is mixed in advance in a batch mode, and the mixture
Is continuously supplied to the granulation step. Preferred granulation conditions in the above-mentioned tumbling granulation method are as follows.
It is shown below. (1) Processing time Processing time for high bulk density in batch type and continuous type
The average residence time defined by the following equation
120 minutes is preferable, 10 to 90 minutes is more preferable, and 1
Particularly preferred is 0 to 40 minutes. The time is less than 5 minutes
In some cases, the bulk density cannot be sufficiently increased,
If the time exceeds 0 minutes, the productivity may decrease or the particles of the detergent granules may be broken.
Destruction may occur. Tm = (m / Q) × 60 Tm: average residence time (s) m: Detergent granule retention amount in the container rotary mixer (kg) Q: Capacity in continuous operation (kg / hr) (2) Froude number (Fr) The Froude number defined by the following equation is 0.01 to
It is preferable to select a condition that results in 0.8. The conditions
Is preferably from 0.05 to 0.7, more preferably from 0.1 to 0.
65 is more preferred. The Froude number is less than 0.01
, It is not possible to obtain uniform and high bulk density detergent particles.
On the other hand, if it exceeds 0.8, the drum type mixer
In some cases, detergent granule particles may be scattered, causing normal shear mixing.
May not occur. Formula: Fr (Froude number) = V²/ (R × g) V: Peripheral speed (m / s) at the outermost periphery of the container rotary mixer R: radius from the center of rotation of the outermost periphery of the container rotary mixer
(M) g: Gravitational acceleration (m / s²) (3) Volume filling rate (x) The volume filling ratio (x) defined by the following formula is 15 to 50%
It is preferable to select the condition that satisfies The conditions include:
20-45% is preferred, 25-40% is more preferred
No. When the volume filling ratio is less than 15%, the productivity is reduced.
On the other hand, if it exceeds 50%, good shear mixing
There may not be a match. x = (M / ρ) / V × 100 M: Amount of detergent granule particles charged to the container rotary mixer
(G) ρ: bulk density (g / L) of detergent granule particles V: Volume (L) of the container rotary mixer For the production of detergent particles in the above-mentioned tumbling granulation method
Here, a batch type or a continuous type may be used. Continuous detergent
Close to plug flow (extrusion flow) to produce particles
It is preferable to use a mixer having mixing characteristics. This place
Raw material from one side (the flat plate on the side of the container rotary mixer)
It is continuously supplied, transferred in a flow system and the other end (container rotating type mixing
It is discharged from the flat plate on the side opposite to the input of the machine. Also,
Direction of lowering the container rotary type mixer from the input side to the discharge side
To facilitate discharge. In this case, the slope
The angle is preferably from 0 to 20 °, more preferably from 0 to 5 °.
Good. If the inclination angle exceeds 20 °, the ungranulated material particles
Children may be mixed. In the case of the continuous type, a container rotating type mixer is used.
To enhance the mixing characteristics closer to the plug flow
, A plurality of partition plates perpendicular to the rotation center line of the container rotation,
Attached at several points in the direction of the rotation centerline, particles on the slope of particle layer
Improves by preventing rolling in the discharge direction when flowing down
be able to. Furthermore, the rotation center line of the container rotary mixer is
Granulation time by having stirring blades on the parallel central axis
Can be shortened. Detergent granule particles are on the slope of the particle layer
By adding agitation to the part where the
Shearing force and impact force are applied to the granular particles, and granulation can be performed in a short time.
The granulation time is shortened. The direction of rotation of the stirring blade is
In the same direction as the rotating direction of the mixer
But the direction opposite to the downward movement of the granulated particles (
Stirring in the same direction), the detergent granulated particles
And the relative speed of the stirring blades increases,
The effect is large and preferable. As the turning radius of the stirring blade,
0.8 times or less the radius of rotation of the rotary mixer is preferred
And 0.7 times or less is more preferable. Rotation of the stirring blade
If the radius exceeds 0.8 times, the inner wall of the rotary mixer
And the distance between the stirring blades is small, and it is strong against detergent granulated particles.
Shear force is applied, and as a result, the detergent granule particles disintegrate,
A situation may occur where granulation is prevented. The tip speed of the stirring blade is 1 to
6 m / s is preferable, and 2.5 to 5 m / s is more preferable.
No. If the tip speed is less than 1 m / s, the detergent
In some cases, sufficient agitation may not be given to the granular particles.
On the other hand, if it exceeds 6 m / s, the detergent granules
Granulation may be hindered. As the shape of the stirring blade in the continuous type,
Has a mixing characteristic close to the plug flow of a container rotary mixer.
Preferably, they do not significantly impede. For example, a container
Of bar-shaped or plate-shaped blades parallel to the rotation center line of the rotary mixer
Format and the like. Mixing characteristics close to plug flow
Product, the residence time distribution width of the product increases,
Detergent particles and non-granulated particles are mixed
As a result, particles that contain a large amount of ungranulated
is there. In the case of the continuous type, the detergent of the rotary mixer
By adjusting the number of stirring blades in the direction of granulated material flow
Thus, granulation can be controlled. In addition, adding fine powder at the time of granulation
Thereby, re-granulation and aggregation are prevented. Specifically, primary grains
Particles having an average particle size (mass average particle size on a sieve) of 10 μm or less
It is preferable to add fine powder, and the amount of the fine powder
0.1 to 1 part by mass per 100 parts by mass of the detergent granules.
0.0 parts by mass is preferable, and 0.2 to 5.0 parts by mass is more preferable.
preferable. By adding such fine powder, detergent
Adhesion on the surface of the granular particles is suppressed, and good powder properties are washed.
Agent particles are formed. The addition amount exceeds 10.0 parts by mass
Of the detergent granules due to excessive fine powder
And the resulting reduction in granulation efficiency may occur. The average particle size of the primary particles of the fine powder (sieve)
Mass average particle size) is a method using light scattering, for example,
By Particle Analyzer (manufactured by Horiba, Ltd.)
It is also measured by microscopic observation. As the fine powder, known fine powders may be used.
It is good. Also, detergent granulated particles and container rotating type mixer
Low wall friction coefficient between inner wall and detergent granules
If it is difficult to apply sufficient ascent,
By mounting multiple baffles on the
The movement is preferably performed. As the height of the baffle
Is a view that does not hinder the movement of particles flowing down the slope of the particle layer.
From the point, 0.25 times or less the radius of rotation of the container rotary mixer
preferable. In the above-mentioned tumbling granulation method, it is preferably used.
Examples of the device include the following container rotating type mixer.
You. (1) Batch type device Mixing is performed by rotating a V-shaped mixing tank.
Format mixer. Example 1: V-type mixer [manufactured by Fuji Paudal Co., Ltd.] Example 2: V-type mixer [manufactured by Seishin Enterprise Co., Ltd.] Mixing is performed by rotating a cylindrical mixing tank.
Format mixer. Example 1: Rocking mixer (Aichi Electric Trading Co., Ltd.) Example 2: Doria coater [manufactured by Powrex Corporation] Example 3: Rotary mixer [Maywa Kogyo Co., Ltd.] Example 4: Drum mixer [Sugiyama Heavy Industries Ltd.] The mixing is performed by the rotation of the double cone type mixing tank.
A form of mixer to do. Example 1: W type mixer [manufactured by Seishin Enterprise Co., Ltd.] Example 2: Double cone mixer (ASR) A cylindrical mixing tank rotates and revolves to mix.
Mixer of the form to perform the combination. Example 1: Dyna mixer [Mori Machinery Co., Ltd.] Example 2: Cross rotary mixer [Maywa Kogyo Co., Ltd.] (2) Continuous type apparatus Mixing is performed by rotating a cylindrical mixing tank.
Format mixer. Example 1: Rocking mixer (Aichi Electric Trading Co., Ltd.) Example 2: Doria coater [manufactured by Powrex Corporation] Detergent particles granulated by the tumbling granulation method
Is classified as necessary to produce only detergent particles of the desired particle size.
It can also be used for goods. Generally known as a classifier
Any of the classifiers can be suitably used,
A sieve can be suitably used. Among them, a suitable sieve is
Gyro sieves, flat sieves, vibrating sieves and the like can be mentioned.
Gyro-type sieves have a slightly inclined flat
A sieve that gives a flat circular motion. Flat sieve is slightly inclined
Sieve that gives reciprocating motion almost parallel to the plane
It is. A vibrating sieve is a device that vibrates rapidly in a direction
It is a sieve that gives movement. The time for sieving is small.
Desirably, it is at least 5 seconds. In addition, sieving efficiency
It is also preferable to use a tapping ball to improve
is there. A specific example of such a sieve is gyrosif
Tar (Tokuju Kosakusho Co., Ltd.), Lotex Screener
(Seishin Enterprise Co., Ltd.), Dalton vibrating screen (Da Co., Ltd.)
Luton) and the like. The vibration caused by the sieve is 6
0 to 300 times / minute is preferable, and 100 to 2500 times / minute.
Is more preferable, and 150 to 2000 times / minute is more preferable.
No. When the frequency of the sieve is less than 60 times / minute, the classification effect is obtained.
The result may be worse, but more than 3000 times / minute
In this case, dust generation may increase. -Average particle size of detergent particles- As the average particle size of the detergent particles (mass average particle size on the sieve)
Is preferably 200 to 1500 μm, and 300 to 100 μm.
0 μm is more preferred. The average particle size is less than 200 μm.
If it is full, it may be easy to generate dust.
If it exceeds, the solubility may be deteriorated. In the present invention, the average particle size (sieve)
Upper mass average particle size) is a value measured by the following method
is there. << Measurement of average particle size (mass average particle size on sieve)
Determination method >> For each sample and its mixture, open
1680 μm, 1410 μm, 1000 μm, 710 μm
m, 500 μm, 355 μm, 250 μm, 150 μ
m, using a sieve of 8 stages and a saucer, classifying
Was. Classification is performed by opening the sieve with a small opening on the tray.
The sieves are stacked in the order of larger sieves, and the top opening 168
100g / time base sample from 0μm sieve
, Cover and cover with a low tap sieve shaker (Iida Co., Ltd.)
Manufactured by tapping: 156 times / minute, rolling: 2
90 times / min), and after shaking for 10 minutes,
The remaining sample on the sieve and pan
Recovery operation was performed. By repeating this operation
1410 to 1680 μm (1410 μm.o
n), 1000 to 1410 µm (1000 µm.o
n), 710-1000 μm (710 μm.on), 5
00 to 710 μm (500 μm.on), 355 to 50
0 μm (355 μm.on), 250-355 μm (2
50 μm. on), 150-250 μm (150 μm.
on), each of dish to 150 μm (150 μm.pass)
A classified sample having a particle size was obtained, and the mass frequency (%) was calculated.
Next, the first opening at which the calculated mass frequency becomes 50% is
aμm, and the size of the sieve opening one step larger than aμm
Is bμm, and mass frequency from tray to sieve of aμm
And the mass frequency on a sieve of a μm is d%.
Then, the mass 50% diameter is obtained by the following formula, and the mass on the sieve is calculated.
The average particle size was used. Formula: Average particle size (50% mass diameter) = 10
^{(50- (cd / (logb-loga) × logb)) / (d / (logb-loga))} [Other Particles] The above-mentioned granular detergent composition of the present invention
Other components that can be included in the product include
Various additives for improving various functions are included. Said that
Other components include those described in the above-mentioned “detergent particles”.
Other components, namely optical brighteners, enzymes, bleaching bases, bleaching
In addition to activators, etc., fragrances, dyes, pigments, etc.
Agent particles '' independently from the granular detergent composition.
Can be. The enzyme is currently used in granular clothing detergents.
It is possible to use commercially available enzyme granules as they are
it can. Examples of the enzyme include Savinase 18T,
Cannase 12T, Lipolase Ultra 50T, Ebara
-8T (above, Novo Nordisk), Maxacal 4
5G, Maxapem 30G, Properase 1000E (hereinafter referred to as
And Dienencor). These enzyme condyles
Substantially no fine powder of 150 μm or less in the grains
(Normally 0.1 mass% or less.) The granular detergent set
In the product, the content of the enzyme granules is 0.1
-5% by mass is preferred, and 0.3-2% by mass is more preferred.
No. The dyes and pigments may be used as fluorescent brightener granules,
Used for coloring the surface of elementary granules, detergent granules, etc.
Can be. The dyes and pigments are dyed on clothes during washing.
It is necessary to use something that does not cause the problem. Such a dye
Pigments, for example, ultramarine, Koranil Green C
G-130 (CI number: 74260), food color red
Color No. 102, Acid Dye Acid Yellow 141, etc.
Can be These dyes and pigments were used as aqueous solutions and dispersions.
After that, stirring granulation similar to the granulator used when producing detergent granules
Various kinds of granules are agitated and tumbled in a mill or tumbling granulator.
However, it can be added and colored. Also various condyles
While transferring the particles on a belt conveyor, the aqueous solution
Alternatively, the dispersion may be sprayed on the granules and colored. Said
The amount of the dye and pigment relative to the granules is
Is preferably about 0.01 to 1% by mass.
No. The bleaching base, percarbonate, is
Sodium carbonate is particularly preferred. The sodium percarbonate, etc.
Is preferably used after coating. Covered
Sodium percarbonate is converted into sodium percarbonate particles, boric acid
Solution and alkali metal silicate are sprayed separately and dried
Can be granulated. At this time, two or more spray nozzles
It may be sprayed separately, simultaneously or sequentially from the chili. E
As the solution of the uric acid and the solvent of the alkali metal silicate,
Water is preferred in terms of solubility, safety, and price. The hoe
Examples of the acid include orthoboric acid, metaboric acid, and tetraboric acid.
Used. In addition, as alkali metal silicates,
Sodium silicate, sodium orthosilicate, water glass
No. 1, No. 2, No. 3 sodium salt, potassium metasilicate
And potassium orthosilicate. They are,
One type may be used alone, or two or more types may be used in combination.
No. Among these, water glass No. 1, No. 2 and No. 3 are liquid
Which is preferable from the viewpoint of convenience in use. other than this,
A conventionally known stabilizer such as a chelating agent is used as a coating agent.
You may use together. The coated sodium percarbonate particles
As a particle diameter (mass average particle diameter on a sieve) of 100 to 20
00 μm is preferable, and the stability and
From the viewpoint of solubility and solubility, 200 to 1000 μm is more preferable.
No. In the granular detergent composition, the percarbonate
The content of sodium is preferably 1 to 30% by mass.
And 2 to 20% by mass is more preferable. As the bleaching activator, tetraacetyl
Ethylenediamine, alkanoylo having 8 to 12 carbon atoms
Xibenzene sulfonic acid, carboxylic acid and their salts
And the like. Among them, the following general formula (IX)
And bleaching represented by at least one of the general formula (X)
Activators and the like are preferred. General formula (IX): Embedded image General formula (X): Embedded image In the general formulas (IX) and (X), R¹
And R²Is independently an alkyl group having 7 or more carbon atoms or
Ph represents a phenyl group, M represents a salt,
Represents a forming cation or hydrogen. In the general formulas (IX) and (X), R¹
Represents an alkyl group or alkenyl having 7 to 17 carbon atoms
Groups are preferred, linear alkyl groups are particularly preferred, and carbon
Most preferred are linear alkyl groups of the formulas 9 to 15. R²When
Is an alkyl or alkenyl group having 7 to 17 carbon atoms
Are preferred, and a linear alkyl group is particularly preferred, and the number of carbon atoms is
Most preferred are 9 to 15 linear alkyl groups. As M
Is an alkali metal such as hydrogen, sodium, potassium, etc.
Amines such as ammonium and alkanolamines;
And hydrogen, an alkali metal and the like are preferred. The general formula (I
In X) and (X), SO₃M group and COOM group
Can be in the ortho, meta or para position,
The la-position is preferred. Use the bleach activator alone
Or two or more of them may be used in combination. These bleach activators can be prepared by a conventional production method.
The average particle size (mass average particle size on the sieve) is about 100 to
As it can be obtained as a 1000μm plate crystal, if necessary
The average particle size will be smaller than 800 μm according to the conventional method.
Pulverize. The average particle size is about 250 to 750 μm
It is preferable to pulverize so that Furthermore, storage stability
Solid at room temperature for the purpose of improving
Tylene glycol (Example: PEG # 3000 to # 2000
0) is heated and melted, and after the bleaching activator is dispersed,
Create a noodle bleach activator with a diameter of about 1 mm
Make granules, then lightly pulverize to about 1-3mm in length
You may use it after doing. At this time, the average particle size was 150 μm.
Preferably, the following fines are virtually absent:
No. In the granular detergent composition, the bleaching activity
The content of the activating agent is preferably 0.5 to 15% by mass.
And 1 to 10% by mass is more preferable. [0109] The above-mentioned fragrance may be a detergent granule alone, a disintegrant granule alone.
Scented on either Germany or a mixture of both
Is also good. As the fragrance used, for example, aliphatic carbonized
Hydrocarbons such as hydrogen, terpene hydrocarbons and aromatic hydrocarbons
, Aliphatic alcohols, terpene alcohols, aromatic alcohols
Alcohols such as alcohol, aliphatic ethers, aromatic
Ethers such as tel, aliphatic oxides, terpenes
Oxides, such as aldehydes, aliphatic aldehydes,
Thiophene such as lupen aldehyde, hydrogenated aromatic aldehyde, etc.
Aldehydes such as aldehydes and aromatic aldehydes, fats
Aromatic ketone, terpene ketone, hydrogenated aromatic ketone, fat
Aromatic cyclic ketone, non-benzene aromatic ketone, aromatic keto
Ketones, acetal, ketals, phenol
, Phenol ethers, fatty acids, terpene-based cals
Bonic acid, hydrogenated aromatic carboxylic acid, aromatic carboxylic acid, etc.
Acids, acid amides, aliphatic lactones, macrocyclic lactones
, Terpene lactone, hydrogenated aromatic lactone, aroma
Lactones such as aliphatic lactones, aliphatic esters, furan
Carboxylic acid esters, aliphatic cyclic carboxylic esters
, Cyclohexylcarboxylic acid ester, terpene
Carboxylic acid esters, aromatic carboxylic acid esters, etc.
Stels, nitromsks, nitriles, amines, pyridis
Nitrogenation of amines, quinolines, pyrrole, indole
Compounds and other synthetic flavors, and natural products obtained from animals and plants
Contains at least one of flavors, natural flavors and synthetic flavors
And the like. One kind of these fragrances
Or two or more of them may be used in combination. As the fragrance, for example,
Motoichi Indo, published by Gaku Kogyo Nippo, Inc.
Sense, ”1969, MONTCLAIR, N. J. Published ST
"Perfume" by EFFEN Arctandel
and Flavor Chemicals "
And the like. Below are specific examples of major fragrance names
Show. Aldehydes C6-C12, Anisaldehyde
C, Acetal R, Acetophenone, Acetyl Cedre
, Adoxal, allyl amyl glycolate, allyl
Cyclohexane propionate, α-damascon, β-
Damascon, δ-damascon, ambrette lid, a
Ambroxane, amylcinnamic aldehyde, amyl
Cinamic aldehyde dimethyl acetal, amylva
Lelianate, amyl salicylate, isoamyl acetate
, Isoamyl salicylate, ouranthiol, a
Cetyljugenol, bacdanol, benzyl acetate
G, benzyl alcohol, benzyl salicylate, bell
Gamyl acetate, bornyl acetate, butyl butyrate
Rate, p-tert-butylcyclohexanol,
p-tert-butylcyclohexyl acetate, o
-Tert-butylcyclohexanol, o-tert
Butylcyclohexyl acetate, benzarde
Hide, Benzyl Formate, Caryophyllene, Kash
Melan, carvone, cedroambar, cedrill acetate
, Cedrol, Celestrid, Dynamic Arco
, Cinnamic aldehyde, cis jasmon, cit
Lal, citral dimethyl acetal, citrusa
Le, citronellal, citronellol, citronellilla
Acetate, citronellyl formate, citronellil ni
Toril, cycla set, cyclamenaldehyde, cycla
Prop, caron, coumarin, cinnamyl acetate
G, δ-C6-C13 lactone, dimethylbenzyl car
Binol, dihydrojasmon, dihydrolinalool,
Dihydromyrcenol, Dimethol, dimyrcetol, diphenyl
Oxide, ethyl crocodile, jugenol, fluite
G, fentyl alcohol, phenylethylphenyl
Acetate, garaki solid, γ-C6-13 lacto
, Α-pinene, β-pinene, limonene, myrcene, β
-Caryophyllene, geraniol, geranyl acetate
G, geranyl formate, geranyl nitrile, heady
ON, Helional, Heliotropin, cis-3-hex
Senol, cis-3-hexenyl acetate, cis-
3-hexenyl salicylate, tripral, hexyl
Lucinamic aldehyde, hexyl salicylate, arsenic
Hyacinth dimethyl acetal, hydrotropic
Cole, hydroxycitronellal, indole, io
Non, isobornyl acetate, isocyclocitral
, Iso E Super, Iso Yugenol, Isononyl Ace
Tate, isobutylquinoline, jasmar, jasmo
Lactone, Jasmofilan, Koa Bon, Rigstra
, Liliar, lime oxide, linalool, lina
Roll oxide, linalyl acetate, liral, ma
Zanzanate, mayol, menthanyl acetate,
Sonsonate, methyl anthranilate, methyl yugenau
, Menthol, α-methylionone, β-methylion
Non, γ-methylionone, methylisoeugenol,
Chill lavender ketone, methyl salicylate, mugue
Aldehyde, mugol, musk TM-II, musk 78
1, Musk C14, Muscon, Civeton, cyclopentadecanone, cyclo
Hexadecenone, cyclopentadecanolide, ambre
Toride, cyclohexadecanolide, 10-oxahexa
Decanolide, 11-oxahexadecanolide, 12-oxa
Hexadecanolide, ethylene brush rate, ethylene oxide
Decanedioate, oxahexadecene-2-one, 1
4-methyl-hexadecenolide, 14-methyl-hexa
Decanolide, musk ketone, musk tibetin, nopirua
Rucol, nopyr acetate, neryl acetate, nero
, Methylphenylacetate, miracaldehyde
Do, neobergamate, oak moss No.1, oribo
, Oxyphenylone, p-cresyl methyl ether
, Pentalide, phenylethyl alcohol, phenyl
Leethyl acetate, alpha pinene, rubafran, da
Macenon, raspberry ketone, dimethylbenzyl carb
Nil acetate, jasmacyclene, methyl naphthyl
Ketone, rose phenone, rose oxide, sandalo
A, Sandera, Santa Rex, Stillar Acetate
G, styryl propionate, terpineol, ta
-Pinyl acetate, tetrahydrolinalool, tet
Lahydrolinaryl acetate, tetrahydrogela
Niol, tetrahydrogeranyl acetate, tona
Lid, traseolide, tripral, thymol, wa
Nirin, Belldox, Yarayara, Anise oil, Bay oil,
Boad rose oil, cananga oil, cardamom oil, cassia
Oil, cedarwood oil, orange oil, mandarin oil, tan
Gelin oil, basil oil, nutmeg oil, citronella oil, oil
Robe oil, coriander oil, elemi oil, eucalyptus oil, fu
Ennenel oil, galvanum oil, geranium oil, hiba oil, cypress
Oil, Jasmine oil, Lavandin oil, Lavender oil, Remo
Oil, lemongrass oil, lime oil, neroli oil, oakmo
Oil, cocoa oil, patchouli oil, peppermint oil, peri
La oil, Petit glen oil, pine oil, rose oil, rose mari
-Oil, cerebral oil, fragrance oil, clary sage oil, sandals
Wood oil, spearmint oil, spike lavender oil, oil
Teranise oil, thyme oil, tonka bean tincture, turpentine
Oil, crocodile bean tincture, vetiver oil, ylang-ylang oil,
Rape fruit oil, citron oil, benzoin, Peruvian balsa
Oil, tuberous oil, oak moss
Solut, Farbal Sam, Mustinki, Castri
Um tincture, civet tincture, ambergris tincture, etc.
Is mentioned. These may be used alone,
Two or more kinds may be used in combination. Solvent or retention agent for the fragrance
As, for example, diethyl phthalate, dipropylene
Glycol, benzyl benzoate, isopropylamine
Restate, Herculin, Isopentane, Orangetel
Pens and the like. The above-mentioned fluorescent whitening agent was added to detergent granules as described above.
Independently of the particles, contained in the granular detergent composition of the present invention.
, For example, granular sodium carbonate, fine powder type A Zeola
The fluorescent brightener powder together with the
Kinetic or stirring granulation, the optical brightener powder and clay
After mixing the minerals, add water and extrude and granulate, fluidized bed, etc.
For example, and then adding it. The particle size of the fluorescent whitening agent granules is 25
0 to 1000 μm is preferable, and 250 to 750 μm is more preferable.
Is more preferable. In addition, in the granular detergent composition of the present invention,
The content of the optical brightener is the same as the pure content of the optical brightener.
And preferably 0.05 to 2% by mass, and 0.1 to 1% by mass.
% Is more preferred. [0116] Next, the present invention will be described with reference to examples.
The present invention is not limited by these examples.
No. <Preparation of detergent particles> (1) Preparation example 1 of detergent particles Sample Nos. Shown in Tables 2-4. "1-A", "1-
B "," 1-C "," 7-A "," 7-B "," 10-
"A" and "10-B" were prepared as follows. (1-1) Granulation of detergent particles Nonionic surface activity among the detergent particle compositions shown in Table 1 below
(Nonion A, ~ C), auxiliary shown in each section of Tables 2-4
Amount (grinding aid) and amount of coating (surface coating agent)
A-type zeolite equivalent to the above, for dry powder coating
1.1% of zeolite A, enzymes, dyes and fragrances
Components in a 250 L mixing tank (in the case of composition A in Table 4,
Water, fluorescent agent, AOS-K, LAS-K, LAS-Na
(LAS-K and LAS-Na are not included in this formulation.
Ruby benzene sulfonic acid and potassium hydroxide or hydroxide
Those produced by neutralization with sodium. ), Soap, a
Crylic / maleic copolymer, zeolite A, charcoal
Potassium acid, sodium carbonate, sodium sulfite, α-
In the order of SF-Na, in the case of the composition E, water, a fluorescent agent, AO
SK, LAS-K (LAS-K is a linear
Alkylbenzenesulfonic acid and potassium hydroxide
Neutralized. ), Sodium silicate, soap, A
Type zeolite, potassium carbonate, sodium carbonate
200 kg was blended. The slurry has a water content of 38% by mass and a specific gravity.
1.1 to 1.2 kg / L, pH 11 to 11.5
Was. The prepared slurry was used in a countercurrent type, with a tower diameter of 2.0.
m, using a pressurized nozzle in a drying tower with an effective length of 5.0 m.
Feed and spray at a capacity of 00 kg / hr to obtain dry powder
Was. The nozzle is the same as that described in Example 2 of JP-A-9-75786.
And spraying at a spray pressure of 0.25 MPa.
Further, 3.0% of fine powdered zeolite A was entrained from the bottom of the tower.
Blow cold air to lower the powder temperature and
We also did the training. (Hereafter, zeolite is coated
Dried powder is sometimes referred to as “spray-dried particles”.
You. ) At this time, the hot air temperature in the drying tower is 280 ° C and the exhaust air temperature
The temperature is 100 ° C and the temperature of the obtained dry powder is 40 ° C.
there were. Spray-dried particles have an average particle size of 250 μm, bulk specific gravity
0.28 kg / L, angle of repose 40 ° immediately after drying, average moisture
It was 4.0% by mass. [0120] Each of the nonionic interfaces is
Activator and water are continuously kneaded by Kurimoto Iron Works,
KRC-S4 type), kneading capacity 120 kg / h,
Kneading was performed at a temperature of 70 ° C. to obtain an amorphous solid detergent. This
Of irregular shaped solid detergent with a 10 mm hole die
Letter Double (Fuji Powdal Co., Ltd., EXDFJS
-100 type) and cut with a cutter
(Cutter peripheral speed is 5m / s), length is about 5-30mm
A solid detergent pellet was obtained. Next, a pulverization aid was added to the obtained solid detergent.
A zeolite (mass average particle size on a sieve: 1)
80 μm) are shown in Tables 2 to 4 (amount of auxiliary agent (grinding auxiliary agent)).
In series in the presence of cold air (10 ° C, 15 m / s)
Fitzmill (Hosokawa Micron Corporation) arranged in three stages
(Manufactured by DKA-3).
The clean hole diameter and the number of rotations are described in Tables 2 to 4). Finally, a horizontal cylindrical type rolling mixer (cylindrical diameter
585 mm, cylinder length 490 mm, container 131.7 L
20mm clearance between the inner wall of the drum and the inner wall,
With two 45 mm height baffles) and a filling rate of 3
Tables 2-4 under the conditions of 0%, rotation speed 22 rpm, and 25 ° C.
Fine powder A in the amount shown in (Coating amount (surface coating agent))
Add zeolite and roll for 1 minute to modify the surface
Got a child. Sample No. About "7-B",
Gyro shifter manufactured by Tokuju Kousaku Co., Ltd.
Using a GS-C2 type sieve having a mesh size of 405 μm (sieve net)
Area: 0.2391m², 160 mm × 180 mm = 0.
0288m²4 tapping balls with a diameter of 30 mm each
At a rotation speed of 250 rpm.
Detergent particles continuously so that the upper powder layer height is 10 mm
Is supplied and classified, and the detergent particles that do not pass through the sieve (detergent preparation)
(88% by mass in the granules). In addition, a sieve having an aperture of 405 μm
Fine powder (12% by mass in detergent granules) that has passed through
It was supplied to the kneader and reused. Sample N
o. Regarding “9-A”, the obtained detergent particles were opened.
1680 μm, 1410 μm, 1190 μm, 1000
μm, 710 μm, 500 μm, 350 μm, 250 μ
Classification using 9-stage sieves and pans of m and 149 μm
Then, the particle size distribution shown in Table 4 was adjusted. (1-2) Perfume of detergent particles Horizontal cylindrical tumbling mixer (cylinder diameter 585mm, cylinder length
490mm, 131.7L inside of drum inside wall
Baffle plate with 20mm clearance and 45mm height from wall
), At a filling rate of 30% and a rotation speed of 22 rpm.
m, while mixing the detergent particles obtained at 25 ° C.
Spray the amount of perfume shown in 1 (perfume) to perfume detergent particles
did. (1-3) Coloring of detergent particles In order to color some of the obtained detergent particles, a perfumed washing
The agent particles are transported on a belt conveyor at a speed of 0.5 m / s.
Whisk (detergent particle layer height 30 mm on belt conveyor, layer width
Table 1 (Dye)
Was sprayed so as to have the amount shown in FIG. (1-4) Addition of enzyme particles Table 1 (Enzymes)
And the horizontal cylinder type tumbling mixer (cylinder diameter 5
85mm, cylinder length 490mm, container 131.7L
20mm clearance between inner wall and inner wall of ram
With two 45 mm baffles) and a filling rate of 30
%, Rotation speed 22 rpm, and mixed at 25 ° C.
These samples were obtained. (2) Preparation Example 2 of Detergent Particles Sample No. shown in Tables 2 and 3. "2-A", "2-
B "," 2-C "," 4-A "," 4-B ", and" 4-
"C" was prepared as follows. (2-1) Granulation of detergent particles Nonionic surface activity among the detergent particle compositions shown in Table 1 below
Agents (nonionics A to C), coatings indicated in each item of Tables 2 to 3
Type A for surface coating corresponding to the amount of coating (surface coating agent)
Olite, 1.1% type A zeo for dry powder coating
250L of ingredients excluding light, enzymes, pigments and fragrances
In the case of the composition A of Table 4 in the tank, water, a fluorescent agent, AOS-K,
LAS-K, LAS-Na (LAS-K and LAS-Na
Means that linear alkylbenzene sulfonic acid and hydroxyl
Neutralized with potassium hydroxide or sodium hydroxide
Things. ) Soap, acrylic acid / maleic acid copolymer,
A-type zeolite, potassium carbonate, sodium carbonate, sulfite
Sodium acid, α-SF-Na, and
In the case, water, fluorescent agent, LAS-Na (LAS-Na
Of linear alkylbenzene sulfonic acid and hydroxide
Thorium neutralized and produced. ) Sodium silicate
Soap, polyacrylic acid-Na, polyethylene glyco
, A-type zeolite, sodium carbonate, sodium sulfite
Um, sodium chloride, in order of 200kg
Was. The slurry had a water content of 38% by mass and a specific gravity of 1.1 kg /
L, pH 11. The prepared slurry was used in a countercurrent type, with a tower diameter of 2.0.
m, using a pressurized nozzle in a drying tower with an effective length of 5.0 m.
Feed and spray at a capacity of 00 kg / hr to obtain dry powder
Was. The nozzle is described in Example 2 of JP-A-9-75786.
Spray at the spray pressure of 0.25MPa using the same as above
did. Also, 1.1% of fine powdery A zeolite was added from the bottom of the tower.
Blow cold air to lower the powder temperature while drying
Powder coating was also performed. The heat in the drying tower at this time
The wind temperature is 280 ° C, the exhaust temperature is 100 ° C,
The temperature of the dried powder was 40 ° C. Spray-dried particles are average
Particle size 250 μm, bulk specific gravity 0.28 kg / L, immediately after drying
The angle of repose was 40 ° and the average moisture was 4.0% by mass. This jet
The mist-dried particles are supplied to a Ledige mixer (Matsubo Co., Ltd.,
M20 type) (filling rate: 50%) and shown in Tables 2-3.
Stirring was started at the main spindle rotation speed and the chopper rotation speed. Stir
30 seconds after the start of stirring, each nonionic surfactant and water were added.
The mixture was added in 5 minutes, and stirred granulation was performed at 35 ° C under the conditions shown in Tables 2-3.
The process was continued until the average particle size shown in Table 2 was reached. Finally, Tables 2-3
Type A zeolite in the amount shown in (Coating amount (surface coating agent))
Add oleite and stir for 30 seconds to modify the surface and detergent particles
Got. (2-2) Perfume of detergent particles Deodorizing detergent particles in the same manner as in Preparation Example 1 of detergent particles
Was. (2-3) Coloring of detergent particles Detergent particles are colored in the same manner as in Preparation Example 1 of detergent particles,
Partially colored detergent particles were obtained. (2-4) Addition of enzyme particles Shown in Table 1 (enzyme) in the same manner as in Preparation Example 1 of detergent particles.
Enzyme particles (Table 1 composition B, more crystalline
7.6% by weight of silicate).
Obtained. (3) Preparation Example 3 of Detergent Particles Sample No. shown in Table 2 "3-A", "3-B" and
And "3-C" were prepared as follows. (3-1) Granulation of detergent particles Nonionic surface activity among the detergent particle compositions shown in Table 1 below
Agents (nonions A to C), coatings shown in each section of Table 2
A type Zeola for surface coating corresponding to the amount of coating (surface covering agent)
, 1.1% zeolite A for dry powder coating
Ingredients, excluding enzymes, pigments, and fragrances are placed in a 250-L mixing tank
Water, fluorescent agent, AOS-K, LAS-K, LAS-Na
(LAS-K and LAS-Na contain linear alkyl
Benzenesulfonic acid and potassium hydroxide or sodium hydroxide
Thorium neutralized) soap, acrylic
Acid / maleic acid copolymer, zeolite A, potassium carbonate
, Sodium carbonate, sodium sulfite, α-SF-
A total of 200 kg was added in the order of Na. The slurry is moisture 3
8 mass%, specific gravity 1.1-1.2 kg / L, pH 11-1
1.5. The prepared slurry was used in a countercurrent type, with a tower diameter of 2.0.
m, using a pressurized nozzle in a drying tower with an effective length of 5.0 m.
Feed and spray at a capacity of 00 kg / hr to obtain dry powder
Was. The nozzle is described in Example 2 of JP-A-9-75786.
Spray at the spray pressure of 0.25MPa using the same as above
did. Also, 1.1% of fine powdery A zeolite was added from the bottom of the tower.
Blow cold air to lower the powder temperature while drying
Powder coating was also performed. The heat in the drying tower at this time
The wind temperature is 280 ° C, the exhaust temperature is 100 ° C,
The temperature of the dried powder was 40 ° C. Spray-dried particles are average
Particle size 250 μm, bulk specific gravity 0.28 kg / L, immediately after drying
The angle of repose was 40 ° and the average moisture was 4.0%. This dry grain
A horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylindrical
490mm length, 131.7L container inner wall of drum
20mm clearance with inner wall, 100mm height
(With 6 baffles) (filling rate 50%) 2
Rolling at the rotational speed shown in Table 2 was started under the condition of 5 ° C. Stir
60 seconds after the start of stirring, spray each nonionic surfactant and water
And tumbling granulation until the average particle size shown in Table 2 is reached
Was done. Finally, see Table 2 (Coating amount (surface covering)
A) zeolite in the amount shown in (1)) was added and stirred for 30 seconds.
The mixture was stirred and surface-modified to obtain detergent particles. (3-2) Perfume of detergent particles Deodorizing detergent particles in the same manner as in Preparation Example 1 of detergent particles
Was. (3-3) Coloring of detergent particles Detergent particles are colored in the same manner as in Preparation Example 1 of detergent particles,
Partially colored detergent particles were obtained. (3-4) Addition of enzyme particles In the same manner as in Preparation Example 1 of detergent particles, the results are shown in Table 1 (enzyme).
Add the enzyme particles of the blended amount
Obtained. (4) Preparation example of bleach activator particles Sample No. shown in Table 3 "5-A" and "5-B"
Was prepared as follows. (4-1) Granulation of Bleaching Activator Particles Of the compositions shown in Table 1, the amount of auxiliary (powder) shown in each item of Table 3
Excluding A-type zeolite for grinding aids
All raw materials are extruded by Hosokawa Micron Corporation
・ Put into Ohmix EM-6, 65 ℃, 160r
0.8m by kneading and extruding under pm conditions
An noodle extruded product of mφ was obtained. This extruded product
With a screen equipped with a screen with a hole diameter of 10 mmφ
Kneading and pressing with a tar FXB type (Fuji Powder Co., Ltd.)
Cold air at 15 ° C from the same direction as the
Introduced and pulverized in the amount shown in Table 3 (Auxiliary Amount (Pulverizing Aid))
Auxiliary agent (fine zeolite A) was supplied in the same manner
Each sample was obtained by crushing at the rotation speed shown in 3.
Was. (5) Preparation Example of Bleach Component Particles Sample No. shown in Table 4 "8-B" and "8-C"
Was prepared as follows. (5-1) Mixing of bleach particles (4) Bleaching activation obtained in Preparation Example of Bleaching Activator Particles
Agent particles (in Table 3, sample Nos. “5-A” and “5-A”).
B ") and bleach particles (in Table 4, sample No." 8-
A ") and a horizontal cylinder so that the mass ratio shown in Table 4 is obtained.
Type tumbling mixer (cylinder diameter 585mm, cylinder length 490m)
m, 131.7 L of the drum inner wall surface with the inner wall surface
Has two baffles with 20mm clearance and 45mm height
), Filling rate 30%, rotation speed 22rpm
m, mixed at 25 ° C to obtain each sample
Was. (6) Preparation Example 4 of Detergent Particles Sample No. shown in Table 3 "6-A", "6-B" and
And "6-C" were prepared as follows. (6-1) Granulation of detergent particles The nonionic surfactant has a composition shown in Table 1 below.
(Nonionics A to C), coating amount in Table 3 (surface
A) zeolite A, enzyme, pigment,
And all ingredients except fragrance
(M20, manufactured by Matsubo Corporation) (filling rate: 50
%) And the spindle speed and chopper speed shown in Table 3
Stirring was started. 30 seconds after the start of stirring, each nonion
Surfactant and water are added in 2 minutes, and at 30 ° C.,
Agitation granulation was continued until the average particle size shown in Table 3 was reached.
Finally, the results are shown in Table 3 (coating amount (surface covering agent)).
Minutes of A-type zeolite and stirred for 30 seconds
Modification gave detergent particles. (6-2) Perfume of detergent particles Deodorizing detergent particles in the same manner as in Preparation Example 1 of detergent particles
Was. (6-3) Coloring of detergent particles Detergent particles are colored in the same manner as in Preparation Example 1 of detergent particles,
Partially colored detergent particles were obtained. (6-4) Addition of enzyme particles In the same manner as in Preparation Example 1 of detergent particles, the results are shown in Table 1 (enzyme).
Add the enzyme particles of the blended amount
Obtained. (7) Preparation Example 7 of Detergent Particles Sample No. shown in Table 4 Adjust "9-A" as follows
Made. Of the detergent particle compositions shown in Table 1 below, Table 4
Coating amount (surface covering agent))
Water, fluorescent agent, AOS
-K, LAS-K, LAS-Na (LAS-K and LAS
-Na is a linear alkylbenzene sulfonic acid
And neutralized by potassium hydroxide or sodium hydroxide
Produced) soap, acrylic acid / copolymaleic acid
A, zeolite A, potassium carbonate, sodium carbonate
, Sodium sulfite and α-SF-Na in this order for a total of 20
0 kg was blended. The slurry had a water content of 38% by mass and a specific gravity of 1.
It was 1 kg / L and pH 11. Apply the prepared slurry
Flow type, tower diameter 2.0m, effective length 5.0m
Feeding and jetting at a capacity of 400 kg / hr using a chisel
A mist was obtained to obtain a dry powder. The nozzle is the one described in JP-A-9-75786.
The same thing as described in Example 2 was used, and the spray pressure was 0.25MP.
a. In addition, fine powdered A-ze
Blow cold air accompanied by 1.3% of olite to lower the powder temperature
At the same time as coating the dried powder,
Got. The hot air temperature in the drying tower at this time was 280 ° C,
The temperature is 100 ° C. and the temperature of the obtained dry powder is 40 ° C.
Met. Spray-dried particles have an average particle size of 250 μm, bulk specific gravity
0.28 kg / L, angle of repose 40 ° immediately after drying, average moisture
It was 4.0%. [0145] [Table 1] * The composition is shown purely. [0146] [Table 2]In the table, “* 1” is arranged in three stages in series.
Indicates the number of rotations (%) of the crusher (first stage / second stage / third stage)
(100% = 4700 rpm). Also "* 2"
Is a crusher arranged in three stages in series (first stage / second stage / 3 stage)
Eye) indicates the hole diameter [mm] of the screen. [0148] [Table 3][0149] [Table 4]In the table, “* 1” is arranged in three stages in series.
Indicates the number of rotations (%) of the crusher (first stage / second stage / third stage)
(100% = 4700 rpm). Also "* 2"
Is a crusher arranged in three stages in series (first stage / second stage / 3 stage)
Eye) indicates the hole diameter [mm] of the screen. (Examples 1 to 17 and Comparative Examples 1 to 3)
Table 5 shows the sample particles obtained by the method.
According to the blend ratio (% by mass) shown in
Flat cylindrical tumbling mixer (cylinder diameter 585 mm, cylinder length 4
90mm, inner wall on drum inner wall of container 131.7L
A baffle with a clearance of 20 mm from the surface and a height of 45 mm
2 sheets), filling rate 30%, rotation speed 22
The mixture was mixed under the conditions of rpm and 25 ° C. The resulting mixture is below
Evaluation was performed according to the measurement method described above. The results are shown in Tables 5 and 6.
You. <Measurement of Tensile Rupture Stress> Hosokawa Micron
Gold that can be divided into two parts vertically using an Agu robot
Cell made of genus (cell inner diameter 25 mm x height 37 mm)
, 15 g of each sample and a mixture thereof was charged, and the temperature was 2
0 ° C, maximum compression force 980N (maximum compression pressure 2.0MP
a), holding time 0 seconds, compression speed 1.0 mm / sec
Compression, tension spring wire diameter 1.2mm, tension speed 0.4
Pull only the upper cell under the condition of mm / sec and 20 ° C.
The maximum tensile stress when the cell breaks up and down
Stress [Pa] was set. <Average particle size and rosin
Measurement of tilt Z (1) Measurement of average particle size For each sample and its mixture,
m, 1410 μm, 1000 μm, 710 μm, 500
μm, 355 μm, 250 μm, 149 μm
The classification operation was performed using a sieve and a saucer. Classification operation
Is a small sieve with a large opening
In the order of 1680 μm
100 g / time of base sample
Tap-type sieve shaker (Tappin, manufactured by Iida Manufacturing Co., Ltd.)
(156 times / minute, rolling: 290 times / minute)
After shaking for 10 minutes, on each sieve and saucer
Operation to collect the sample remaining in the
Was. By repeating this operation, 1410-1
680 μm (1410 μm.on), 1000 to 141
0 μm (1000 μm.on), 710 to 1000 μm
(710 μm.on) 500 to 710 μm (500 μm
m. on), 355-500 μm (355 μm.o.
n), 250-355 μm (250 μm.on), 15
0 to 250 μm (150 μm.on), dish to 150 μm
(150μm.pass)
The mass frequency [%] was calculated. Next, the calculated mass frequency becomes 50% or more.
The opening of the first sieve is a μm, and
The sieve size of the next larger sieve is set to bμm, and aμ
Integrate the mass frequency up to the sieve of m in c%, on the sieve of aμm
Is defined as d%, the following equation gives (mass 50%
Diameter). Formula: Average particle size (mass 50% size) (mass average particle size on sieve)
= 10^{(50- (cd / (logb-loga) × logb)) / (d / (logb-loga))} (2) Slope in rosin Lambra plot
Measurement of Z The average particle size calculated by the above method is less than 710 μm
In the case, 710 μm. on, 500 μm. on, 355
μm. on and 250 μm. and the mass frequency Y of on
Let X be the opening of each sieve, and log X of X
Plot log / log (100 / Y)
A small square approximation straight line was obtained, and the slope of the straight line was set as Z.
When the average particle size is 710 μm or more, 1000 μm
m. on, 710 μm. on, 500 μm. on and 3
55 μm. and the mass frequency of ON, and the opening of each sieve
Is plotted in the same manner as X to obtain a least square approximation straight line.
The slope of the straight line was Z. <Measurement of True Density> Each sample and its mixture
The true density of the material is measured according to JIS M 8717 “Iron ore density measurement
Method 5. Change some measurement conditions according to `` Air comparison method ''
It was measured by: At this time, the granular washing
Since the agent composition originally contains water, the above-mentioned JI
It is necessary to perform drying as described in “5.3 Samples” of S
Absent. <Measurement of Bulk Density> Each sample and its mixture
The bulk density of the product was measured according to JIS K3362. <Classification test> Described in JP-A-7-205978.
Mass frequency of 1000μm · on [%]
Is filled with 1.2 kg of the mixture of
The lid was made of polyethylene. 8 boxes containing this granular detergent
Into one cardboard box, and between Tokyo and Osaka (E
Between Togawa Ward and Sakai City, Osaka), Yamato Transport Co., Ltd.
^(R)2 reciprocations. After the transfer, the granular detergent composition
Unpack the box and gently pour 1 cm of granular detergent
And the mass frequency [%] of 1000 μm · on
It measured and calculated the classification property [-] by the following formula. Formula: Classification [-] = (1000 μm of upper 1 cm after transfer
m · on mass frequency [%]) / (1000 μm ·
on mass frequency [%]) The value of the obtained classification property was evaluated according to the following criteria.
(△ and × are out of tolerance). -Criteria- *: 1.0 to less than 1.2 *: 1.2 to less than 1.4 ・ □: 1.4 to less than 1.6 ・ △: 1.6 to less than 1.8 *: 1.8 or more <Solidification test> Coated cardboard from outside
(Basic weight: 350 g / m²), Wax sand paper (basis weight:
30g / m²), Kraft pulp paper (basis weight: 70g / m
²) Paper with a length of 15 cm and a width of 9.3
A box measuring 1 cm × height 18.5 cm was prepared. Each box in this box
1.2 kg of the mixture of the sample, 40 ° C., 85% RH
After storing in a constant temperature and humidity room for 30 days, the detergent is
Carefully transfer onto a 0μm sieve and gently shake the sieve
After that, determine the mass on the sieve and the total mass, and solidify from the following formula
The sex (%) was quantified. Formula: solidification (%) = ｛weight on screen (g) / total weight
(G)｝ × 100 The obtained solidification value was evaluated according to the following criteria.
(X is out of tolerance). -Criteria- ・ ◎: less than 5.0 ・ ○: 5.0 to less than 10.0 ・ △: 10.0 to less than 15.0 *: 15.0 or more [0161] [Table 5][0162] [Table 6] Raw materials used: α-SF-Na: the following production method
Having a C14-16 alkyl chain obtained by the
Rufasulfo fatty acid sodium (65.6% by mass pure
In addition, 3.28% by weight of methyl sulfate, sodium sulfate
1.31% by mass of lithium, sodium sulfo fatty acid
3.08% by mass of disalt of methanol, 1.51% by mass of methanol,
Unreacted methyl ester 1.21% by mass, water 24.01
amount%). However, the sodium alpha sulfo fatty acid is
In the manufacturing process of the detergent composition, 7% by mass is further added to the detergent.
In the long-term storage of the composition, 25% by mass
It may change to sodium salt of sulfo fatty acid.
You. (Production method) Thin-film reactor (single-tube reactor,
Raw material according to (diameter = 10mm, reactor length = 2.5m)
Methyl myristate (Lion oreochem
(Made by Cal Co., Ltd., pastel M-14) and methyl palmitate
(Lion Oreo Chemical Co., Ltd., Pastel M-1
Fatty acid methyl ester obtained by mixing 6) at a weight ratio of 2: 8
(Iodine value 0.40, molecular weight 264)₃Moth
Liquid SO₃And the dilution gas is
8% by mass SO using nitrogen gas₃Containing inert gas,
Reaction molar ratio (SO₃/ Methyl ester) = 1.2 and gas
The absorption reaction is performed in a thin-film reactor, and after gas-liquid separation, 80
Aging reaction at 60 ° C for 60 minutes, sulfone with a conversion of 97%
The acid was obtained. Then 20% by weight of methanol to sulfonic acid,
35% hydrogen peroxide solution (2% by mass as pure hydrogen peroxide
Sulfonic acid), and after uniform mixing, drift at 80 ° C for 180 minutes.
A white reaction was performed. Then with aqueous sodium hydroxide
Perform neutralization reaction to neutralize 47% concentration (surfactant concentration)
Product, and recycle flash concentration to methanol
(Reused by rectification in a later step), water is evaporated to 65.6
% Concentrated (surfactant concentration) neutralized product was obtained. Color
(5% by mass ethanol solution was passed through a 40 mm optical path length, No. 4
2 Measured with a Krett photoelectric meter using a blue filter
Constant) was 30. ・ LAS-K: Lipon LH-200 (Lion Corporation)
(Purchased in July 2001) ・ LAS-Na: Lipon LH-200 (Lion
(Purchased in July 2001) AOS-K: -14: 1 carbon atoms obtained by the following production method
6: 18 = 15: 50: 35 α-olefin sulfone
Of potassium phosphate and potassium hydroxyalkyl sulfonate
Mixture (pure content 70%, alpha olefin sulfonate potassium)
The ratio of potassium to potassium hydroxyalkyl sulfonate
7: 3, balance is unreacted α-olefin, sodium sulfate
Water, sodium, sodium hydroxide, water, etc.) (Production method) α-olefin (Dialen 14 at 25 ° C)
8, Mitsubishi Chemical Corporation) at a capacity of 970 kg / hr
Successive TO reactors (TO-500, Lion Corporation)
, Film type reactor)₃gas
At about 35 ° C.
α-olefin sulfonic acid and impurities (mainly sultone)
The resulting sulfonate was obtained. This sulfonated product 1370k
g / hr to caustic potash 630 kg / hr (moisture 52
% Aqueous solution) to perform a neutralization reaction, containing impurities
As a result, potassium α-olefin sulfonate was obtained. This impurity
Shell and Chew to hydrolyze sultone in
The temperature is increased to 140 ° C through the heat exchanger.
170 ° C. through 1.4 MPa steam in a reaction tube
To promote hydrolysis. After that, pressure 1MPa
Flash concentration and dehydration to reduce the water content to about 27% by mass.
did. The obtained pure amount of AOS-K is usually 66 to 74 mass.
%, The main component is potassium α-olefin sulfonate (about
70%) and potassium hydroxyalkyl sulfonate (about
30%), the color is (10% solution LK value) 7
0, 1.8% of free alkali (KOH) (vs. AOS-K
Net). AOS-Na: Riporan PJ-400 (Lion
(Purchased in July 2001) ・ AS-Na: Dovanol 25 Sarue manufactured by Mitsubishi Chemical Corporation
Salt (C12-15 sulfate) Soap: fat obtained by the following production method
Sodium acid (Production method) Fatty acid methyl ester (P
Stele MC-O *, manufactured by Lion Oreo Chemical Co., Ltd.)
1576 kg / h, 48% NaOH aqueous solution at 40-60 ° C
Liquid 445 kg / h, water (Lion Chiba Plant Nakasui) 336
kg / h to the mixing pump continuously
110-130 ° C with & tube type heat pre-heater and pre-heater
The saponification reaction was allowed to proceed for 9 to 10 minutes while maintaining (reaction
Rate 99.5 to 99.8%). Then, the overhead pressure is 0.2 to 0.1.
Flash steam with 6 kPa and tower temperature of 98-100 ° C
The reaction product is introduced into the
The ethanol was evaporated. Finally removed the methanol
Soap is introduced into a stirring tank with paddle-type stirring blades and retained
80 ° C while maintaining at 98 ° C with stirring for 140 minutes
Add water and concentrate to a soap concentration of 66-67%.
The degree was adjusted. The soap thus obtained has a pure content of 66.
About 67% by mass, and about 0.01% by mass as an impurity.
Fatty acid, about 0.2% by mass of unreacted fatty acid ester, about
0.2% by weight of NaOH, about 0.4% by weight of methanol
including. Nonionic surfactant A: According to the following production method
Oxidation of Diadol 13 (manufactured by Mitsubishi Chemical Corporation)
Adduct of 15 mol of styrene (Production method) 4 liter autoclave (pressure-resistant glass
13 (Mitsubishi Chemical Corporation)
400 g) and 2.3 g of a 30% by mass aqueous NaOH solution
And the inside of the autoclave is replaced with nitrogen.
(While dehydrating at 100 ° C for 30 minutes)
). Next, maintain the temperature at 180 ° C and the pressure at 3 atm
While ethylene oxide (EO: Mitsubishi Chemical Corporation)
1320 g (average number of moles added: 15).
The reaction between iador 13 and EO was performed. Last 30 minutes
After aging, a nonionic surfactant was obtained. Nonionic surface activity
About 2.0% by weight of PEG, unreacted alcohol
About 0.7% by mass. Nonionic surfactant B: According to the following production method
Of Diadol 13 (produced by Mitsubishi Chemical Corporation)
Adduct of ethylene oxide 15 mol and propylene oxide 3 mol (Production method) 4 liter autoclave (pressure-resistant glass
13 (Mitsubishi Chemical Corporation)
400 g) and 2.3 g of a 30% by mass aqueous NaOH solution
And the inside of the autoclave is replaced with nitrogen.
(While dehydrating at 100 ° C for 30 minutes)
). Next, maintain the temperature at 180 ° C and the pressure at 3 atm
While ethylene oxide (EO: Mitsubishi Chemical Corporation)
1320 g (equivalent to an average added mole number of 15 moles)
And react with Diamond Doll 13 and EO for 30 minutes
Matured. Thereafter, the reaction solution was cooled to a temperature of 120 ° C.
While maintaining a pressure of 3 atm at 120 ° C.
Side (PO: manufactured by Mitsubishi Chemical Corporation) 350 g (average addition
(Corresponding to 3 moles of moles) and the reaction was carried out. last
For 30 minutes to obtain a nonionic surfactant. Nonion
Impurity in surfactant is about 2.0% by mass of PEG, unreacted
Alcohol was about 0.7% by mass. Nonionic surfactant C: According to the following production method
According to pastel M-181 (Lion Oreo Chemical
15 mol adduct of ethylene oxide (Production method) 4 liter autoclave (pressure-resistant glass
M-181 (Lion)
400g) and catalyst (magnesium aluminum)
Nitride and manganese composite hydroxide in nitrogen atmosphere 800
Aged at 3 ° C for 3 hours to form a composite oxide of Mg / Al / Mn.
1.2g and 40 mass% KOH aqueous solution 0.1
Charge 2 g, replace the inside of the autoclave with nitrogen, and stir.
(While dehydrating at 100 ° C for 30 minutes)
Do). Then, maintain the temperature at 180 ° C and the pressure at 3 atm.
While holding ethylene oxide (EO: Mitsubishi Chemical Corporation)
899 g (equivalent to an average added mole number of 15 moles)
And pastel M-181 (Lion Oreo Chemical
And EO. Finally ripened for 30 minutes
To obtain a nonionic surfactant. Nonionic surfactant
Approximately 2.0% of PEG and approximately unreacted alcohol
0.7%. A type zeolite: Shilton B (Mizusawa Chemical
(Purchased in July 2001) (80% pure) Acrylic / maleic acid copolymer: Aquaric T
L-300 (Nippon Shokubai Co., Ltd., purchased in July 2001)
(40% pure solution) -Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)
Made in July 2001) ・ Sodium carbonate: Light ash (made by Asahi Glass Co., Ltd., 2001)
(Purchased in July) ・ Sodium sulfite: Anhydrous sodium sulfite (Shinshu Chemical Co., Ltd.)
Made in July 2001) ・ Sodium silicate: JIS No. 1 sodium silicate (Nippon Kagaku
Manufactured by Gaku Kogyo Co., Ltd., purchased in July 2001 (45% pure water soluble)
liquid) -Crystalline silicate: SKS-6 (2000, manufactured by Hoechst)
(Purchased in October) ・ Fluorescent agent: Tinopearl CBS-X (Ciba Specialty)
(Made by Chemicals, purchased in October 2000) Bleach particles: sodium percarbonate (Mitsubishi Gas Chemical Co., Ltd.)
(Manufactured by SPC-D, purchased in July 2001) ・ Bleaching activator: 4-decanoyloxybenzoic acid (Mitsui
(Chemical Co., Ltd., purchased in July 2001) -Enzyme particles: Savinase 18T (Novo Nordiscuba)
Io Industry) polyethylene glycol: PE
G6000 (Lion Corporation, purchased in July 2001) -Dye: 35% solution of blue dye solution (ultramarine) (Dainichi Seika)
(Made in July 2001) ・ Fragrance: 0.5% by mass of decanal, 0.3% of octanal
Mass%, hexyl cinnamamide aldehyde 10.0 mass
%, Dimethylbenzylcarbinyl acetate mass 8.0
%, Lemon oil 3.0% by mass, Liliar 6.0% by mass,
Liral 2.0% by mass, linalool 5.0% by mass,
Nylethyl alcohol 7.5 mass%, tonalide 2.0
%, O-tert-butylcyclohexyl acetate
3.0% by mass, galaxolide 50BB 2.0% by mass,
2.5% by mass of Nascol, 1.0% by mass of geraniol,
Citronellol 2.0% by mass, Jasmorandi 2.0 quality
%, Methyldihydrojasmonate 5.0% by mass,
-Pineol 1.0% by mass, methylyonone 3.0%
%, Acetylcedrene 5.0% by mass, lemonitrile 1.
0% by mass, fluate 1.0% by mass, Oribbon 1.5
Mass%, benzoin 1.0 mass%, cis-3-hexeno
0.5% by mass, coumarin 2.0% by mass, damacenone
0.2% by mass, Damascon 0.3% by mass, Helional
1.5% by mass, heliotropin 1.5% by mass, Anisua
2.5% by mass of aldehyde, gamma-undecalactone 0.
8% by mass, 1.2% by mass of bagdanol, tripral
0.5% by mass, stiralyl acetate 1.5% by mass,
0.1% by mass of caron, 3.0% by mass of pentalide,
2.9% by mass of hexadecene-2-one, ethylene brush
Rate 6.2% by mass. "BB" stands for benzylbenzoe.
Means [0171] According to the present invention, classification and solidification can be suppressed.
Can provide a granular detergent composition that is compatible with both
You.

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Claims (1)

Claims: 1. A composition comprising at least two or more types of particles, wherein the total content of particles excluding the type of particles having the highest content is 3 to 50% by mass, A granular detergent composition having a tensile breaking stress of 3000 to 60000 Pa.