JP4667730B2 - Method for treating crystalline alkali metal silicate - Google Patents

Description

The present invention relates to a method for treating a crystalline alkali silicate in which a crystalline alkali metal silicate and water are mixed under a certain condition, a crystalline alkali metal silicate obtained by the treatment method, and the crystalline alkali metal silicate. The present invention relates to a detergent composition comprising More specifically, a treatment method for suppressing the formation of acicular crystals due to decomposition of the crystalline alkali metal silicate, the crystalline alkali metal silicate treated by the method, and a detergent composition containing the crystalline alkali metal silicate About.

  Crystalline alkali metal silicate is a multi-builder that not only provides good alkali buffering action but also has excellent water softening properties (calcium and magnesium scavenging ability). One of the characteristics of crystalline alkali metal silicates is that they have solubility in water, and this characteristic makes it possible to exhibit an alkali buffering action not found in zeolites that are not soluble in water. In addition, since it is soluble in water, it has the advantages of good rinsing properties and low persistence in clothing.

  However, the high solubility in water, which is a characteristic of crystalline alkali metal silicates, is advantageous in terms of alkali buffering capacity, etc., and at the same time, since it has the property of easily absorbing moisture in the air, It is also a drawback that the ion exchange capacity and alkali buffer capacity are likely to deteriorate. In particular, the crystalline alkali metal silicate absorbs carbon dioxide and water, and the crystal phase decomposes, producing new acicular crystals. In addition, a phenomenon occurs in which the acicular crystals decomposed and formed cause cross-linking between the detergent particles and cake the detergent. Therefore, suppression of this phenomenon is an important issue in blending crystalline alkali metal silicates into detergents.

In Patent Document 1, in a system substantially free of moisture, the above acid can be obtained by blending a crystalline alkali metal silicate with an acid precursor of an anionic surfactant capable of taking a lamellar orientation with a nonionic surfactant. A gelled product containing a nonionic surfactant is formed by neutralizing the precursor, and a stirring type mixer using a water-soluble nonionic organic compound having a melting point of 45 ° C. or higher and an average molecular weight of 1000 or higher as a binder. Shows a method for producing crystalline alkali metal silicate granules having excellent caking resistance, such as rolling granulation. However, in this method, the surface area is reduced by granulating the crystalline alkali metal silicate, and since the water-soluble nonionic organic compound acts as a melting point increasing agent, the non-ionic surfactant stains are suppressed. Therefore, it does not suppress the formation of needle crystals that are the main cause of caking when blended with detergent.
Japanese Patent Laid-Open No. 10-158699

  Accordingly, an object of the present invention is to provide a treatment method for suppressing the formation of acicular crystals due to the decomposition of the crystalline alkali metal silicate, as well as the crystalline alkali metal silicate treated by the treatment method, and further the crystal It is to provide a detergent composition containing a functional alkali metal silicate and having good storage stability.

  The present inventors give a needle-like shape by decomposition of the crystalline phase of the crystalline alkali metal salt by performing a treatment of mixing the crystalline alkali metal silicate having a specific composition and water at a constant weight ratio and a constant temperature. It has been found that the formation of crystals can be suppressed. In addition, the present inventors have found that when the crystalline alkali metal salt treated by the treatment method is added to a detergent, the storage stability of the detergent composition, in particular, the caking resistance is improved, and the present invention is completed. It came to.

That is, the gist of the present invention is as follows.
[1] (A) crystalline alkali metal silicate;
(B) water
(B) / (A) = 0.005-0.250 mixed at a weight ratio, and the method for treating a crystalline alkali metal silicate having a particle growth degree of 1.5 or less by mixing,
[2] A crystalline alkali metal silicate obtained by the treatment method according to [1],
[3] A detergent composition containing at least one crystalline alkali metal silicate obtained by the treatment method according to [1], and [4] a liquid surfactant in the surfactant-supporting granule group and the above [1 ] It relates to the detergent composition obtained by mixing with the crystalline alkali metal silicate obtained by the processing method of description.

  By using the present invention, it is possible to obtain a crystalline alkali metal silicate with little acicular crystal formation due to decomposition, and by using such a crystalline alkali metal silicate, a detergent composition having good storage stability is produced. The effect that it can be done is produced.

1. (A) component crystalline alkali metal silicate In this invention, the crystalline alkali metal silicate (henceforth a raw material crystalline alkali metal silicate) used as a process target is an alkali metal silicate, and ion-exchange ability It is preferable that it is dissolved in water and exhibits alkalinity. The ion exchange capacity can be measured, for example, by a method for measuring the Ca ion exchange capacity. The value is not particularly limited, but is preferably 120 to 250 mg / g, and particularly preferably 130 to 250 mg / g. More preferably, it is 140-250 mg / g, and the thing of this area | region is preferable at the point which can be mix | blended with a compact detergent, when using as a Ca ion exchanger for detergents in order to exhibit an effect in a small quantity.

As the raw material crystalline alkali metal silicate having such ion exchange ability, the formula (I):
xM ₂ O.ySiO ₂ .zMeO.wH ₂ O (I)
(In the formula, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg in MeO) / Ca = 0 to 10 and w is 0 to 20.)
A composition represented by the formula is preferred. Examples of the alkali metal silicate having such a composition include sodium metasilicate, potassium metasilicate, powder No. 1 sodium silicate, powder No. 2 sodium silicate and the like. Moreover, crystalline alkali metal silicate described in JP-B-1-41116 is exemplified as an alkali metal silicate having a particularly high ion exchange capacity.

  As a more preferable alkali metal silicate that expresses a higher ion exchange capacity, in the above formula (I), y / x = 1.0 to 2.1, z / x = 0.001 to 1. 0 alkali metal silicates. As the alkali metal silicate having such a composition, a synthetic inorganic builder described in Japanese Patent No. 2525318 is suitable.

Moreover, in this invention, the storage stability can be improved further by using the alkali metal silicate containing potassium. As a composition of such a preferable alkali metal silicate containing potassium, in the above formula (I), y / x = 1.4 to 2.1, z / x = 0.001 to 1 .0 include composition represented by K / Na = 0.09~1.11 in M ₂ O. As such an alkali metal silicate, a crystalline alkali metal silicate described in Japanese Patent No. 2525342 is particularly preferable.

Among these raw material crystalline alkali metal silicates, x = 1, y = 2, z = 0 in the formula, and M = Na are most preferable from the viewpoint of the ability to capture hardness components such as calcium and magnesium. crystalline layered is sodium disilicate _{Na 2 O · 2SiO 2 · wH} 2 O. The crystalline layered sodium disilicate is composed of polymorphic phases of α, β, δ and ε. In commercial products, an amorphous fraction may also be present. Therefore, the value of y in a commercial product may be an odd number or a value including a decimal point. Preferably, y is 1.9 or more and 2.2 or less. The preferred crystalline layered sodium disilicate is α-sodium disilicate in a proportion of 0 to 40% by weight, β-sodium disilicate in a proportion of 0 to 40% by weight, δ-sodium disilicate in a proportion of 40 to 100% by weight. , And consists of an amorphous fraction in a proportion of 0 to 40% by weight. Particularly preferred crystalline layered sodium disilicates are 7 to 21% by weight α-sodium disilicate, 0 to 12% by weight β-sodium disilicate, 65 to 95% by weight δ-disilicate. Sodium, consisting of an amorphous fraction in a proportion of 0-20% by weight. Most preferred is crystalline layered sodium disilicate containing δ-sodium disilicate in a proportion of 80 to 100% by weight.

  As the crystalline alkali metal silicate, the above may be used alone, or several kinds may be mixed and used as a mixture.

2. (B) Component Water (B) component water can be used not only by itself but also optionally in the form of an aqueous solution or aqueous dispersion of alkali metal sulfate, carbonate and silicate. From the viewpoint of cost, it is preferable to use water alone.

  Examples of suitable water include tap water, distilled water, ion-exchanged water, water vapor, deionized water, and industrial water (having few impurities). When a commercial crystalline alkali metal silicate is used as the component (A), the crystalline alkali metal silicate may contain a small amount of water derived from production or storage in advance. However, the water derived from such production does not contribute to the suppression of crystal growth in the crystalline alkali metal silicate because the concentration is too low. In addition, if the storage conditions are poor and a large amount of water has been absorbed, the crystal phase has already begun to decompose, and water is unevenly distributed in the powder surface layer. The effect of suppressing the decomposition of the crystalline phase of the crystalline alkali silicate is low. Therefore, in order to increase the storage stability of the crystalline alkali metal silicate, an operation of mixing water and the crystalline alkali metal silicate under a certain condition is required.

  As the alkali metal salt which is an optional component, lithium, potassium and sodium salts are preferred, and lithium is particularly preferred because of its high water resistance. Accordingly, lithium sulfate, lithium carbonate, and lithium silicate are particularly preferable as optional components of the component (B). Commercially available lithium silicate includes lithium silicate manufactured by Nissan Chemical Co., Ltd. and lithium silicate manufactured by Nihon Chemical Co., Ltd.

  About an arbitrary component, you may contain independently, may contain it in combination, and does not need to contain it. In the case of containing in combination, water and optional components may be mixed with the component (A) one by one in order, or water and optional components may be mixed in advance and then mixed with the component (A). good. In the case where the optional component includes a solid component, it is preferable to dissolve or disperse the solid component in a liquid in advance because the miscibility with the component (A) increases. For example, when an optional component of a powder such as lithium sulfate is contained, it is preferably dissolved in water in advance to form an aqueous solution and then mixed with the component (A). In addition, in the case where the solid optional component is contained more than the solubility in water, it is preferable to perform pulverization because the mixing property is increased. At that time, the powder may be dry pulverized in advance before being dispersed in water, or may be wet pulverized after being dispersed in water. About the grinding | pulverization method, the grinder used for mixing with the (A) component mentioned later can be used.

  The alkali metal salt is preferably 40/60 or less, more preferably 30/70 or less, and still more preferably 20/80 or less, as a weight ratio with respect to water as component (B). Moreover, when mix | blending lithium salt especially, 1/99 or more is preferable from a water-resistant viewpoint.

3. Processing method of raw material crystalline alkali metal silicate The processing method of this invention is mixing the said (A) component and the said (B) component on fixed conditions. The weight ratio of (A) to (B) is (B) / (A) = 0.020 to 0.250, preferably (B) / (A) = 0.005 to 0.250, More preferably, (B) / (A) = 0.005 to 0.100, and still more preferably (B) / (A) = 0.100 to 0.083.

  The mixing method of the component (A) and the component (B) is an essential matter for the present invention, but any method can be used as long as sufficient mixing of both components is guaranteed. good. In addition, since water is contained as an essential component, it is preferable to use a technique of ejecting and spraying a liquid component together during mixing.

  The pulverizing apparatus and mixing apparatus used for intimately mixing the component (A) and the component (B) are not particularly limited, but those shown below are preferably used.

As the pulverizer, a pulverizer described in Chemical Handbook (Edited by Chemical Society of Japan, p.826-838 (1998)) is used, and examples thereof include the following.
(1) An apparatus for pulverizing by pressure or impact force, such as a jaw crusher, a gyratory crusher, a roll crusher, or a roll mill.
(2) A device in which a striking plate is fixed around a rotor that rotates at high speed, and the processed material is pulverized by a shearing force generated by the rotor and the striking plate.
(3) A device that rotates while a roll or a ball is pressed on a ring, and grinds and grinds the processed material between them. Examples include a ring roller mill, a ring ball mill, a centrifugal roller mill, and a ball bearing mill.
(4) A pulverizing apparatus provided with a cylindrical pulverizing chamber, in which balls or rods are placed as pulverizing media in the pulverizing chamber and rotated or vibrated to pulverize the processed material. There is.
(5) A cylindrical crushing chamber is provided, and a grinding medium such as a ball or a bead is placed in the crushing chamber. Equipment includes tower mills, attritors, and sand mills.
(6) A colloid mill or the like is a device that disperses and pulverizes a liquid by flowing a liquid between small-diameter disks rotating at high speed and applying a strong shearing force.

Next, although it is a mixing apparatus, the following are illustrated.
(1) A mixer having a stirring shaft inside the mixing tank and mixing by attaching a stirring blade to the shaft. For example, a Henschel mixer, a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and the like are available.
(2) A continuous mixer composed of a vertical cylinder with a powder inlet and a main shaft with a mixing blade, supported by an upper bearing and free on the discharge side. For example, there is a flexomix mixer (manufactured by POWREC Co., Ltd.).
(3) A continuous mixer in which a raw material is put into an upper part of a disk having a stirring pin, and the disk is rotated at a high speed and mixed by a shearing action. For example, there are a flow jet mixer (manufactured by Powder Research Powtex Co., Ltd.) and a spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.).

  The mixing time is preferably from 1 second to 50 minutes, particularly preferably from 10 seconds to 10 minutes. It is also possible to contact / mix water, an aqueous solution, and an aqueous dispersion with a crystalline alkali metal silicate in a gaseous, vapor, and aerosol-like state without using a mixer.

  When performing the mixing operation, the temperature of the mixture is preferably adjusted to 1 to 28 ° C, preferably 5 to 25 ° C, more preferably 10 to 25 ° C. If it is this range, the quantity which volatilizes water will be restrained to very small quantity, and a crystalline alkali metal silicate can be processed efficiently.

The essence of the present invention is to modify the surface of the component (A) by bringing the component (B) into contact with the surface of the component (A) by the above mixing treatment, and the component (B) becomes a binder (A). Adhering the component particles together is not preferred because the modified surface is reduced. Therefore, it is preferable that the average particle diameter of the component (A) is not changed by the mixing treatment. As a factor expressing the change in average particle diameter, the particle growth degree defined by the formula (2) can be used, and the particle growth degree is preferably 1.5 or less, more preferably 1.3 or less, and 1. 1 or less is more preferable.
Particle growth rate = (average particle diameter of crystalline alkali silicate after treatment) / (average particle diameter of component (A)) Formula (2)

  The average particle diameter of the crystalline alkali metal silicate obtained by such treatment is preferably 1 μm or more, more preferably 5 μm or more, and particularly preferably 7 μm or more from the viewpoints of dispersibility and storage stability. Moreover, from a viewpoint of an ion exchange rate and the dispersibility to water, 300 micrometers or less are preferable, 200 micrometers or less are more preferable, and 100 micrometers or less are especially preferable.

  In the present invention, the average particle diameter of particles such as crystalline alkali metal silicate is the average value of the constant tangential diameter (Ferret diameter) measured by a scanning electron microscope (SEM).

  Moreover, after processing the crystalline alkali metal silicate of this invention by the said mixing operation, you may make this crystalline alkali metal silicate into a granulated material. The average particle size of the granulated product is not particularly limited, but is preferably 1000 μm or less, more preferably 500 μm or less, further preferably 5 to 200 μm, and particularly preferably 5 to 100 μm from the viewpoint of dispersibility in water. It is enough. When granulating, a granulated material can be obtained by pressure-molding the crystalline alkali metal silicate of the present invention using a granulator.

  Examples of the granulator include a granulator using a compression granulation mechanism described in the granulation manual (edited by the Japan Powder Industry Association, pages 173 to 197 (1975)). Specifically, a roll compactor, A briquetting machine, a rotary tableting machine, etc. are preferable. Moreover, you may form the granulated material of a crystalline alkali metal silicate by the method of granulating, adding a share to powder, stirring. Specifically, the production of crystalline alkali metal silicate using Henschel mixer (Mitsui Miike Kogyo Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator (Powrec Co., Ltd.), etc. Granules are formed.

4). Storage Stability of Crystalline Alkali Metal Silicate As one of methods for evaluating the storage stability of crystalline alkali metal silicate treated by the treatment method of the present invention, the crystalline alkali metal silicate is used in a high humidity atmosphere. There is an evaluation method in which the rate of weight increase when stored in is used and the numerical value is used as an index. The rate of weight increase is defined in the examples. The weight increase rate is not particularly limited, but from the viewpoint of the effect of improving moisture absorption resistance, it is preferable that the weight increase rate is lower than that of the untreated crystalline alkali metal silicate. It is more preferable that the value is lower than the point, and it is more preferable that the value is lower than the 1.0 point.

  Furthermore, the storage stability of the crystalline alkali metal silicate can be evaluated based on the amount of needle-like crystals that are newly generated by the crystal phase of the crystalline alkali metal silicate being decomposed. The smaller the amount of acicular crystals produced, the better the caking resistance of the detergent composition obtained using the crystalline alkali metal silicate. The amount of acicular crystals formed is defined in the examples. The value of the amount of such acicular crystals formed is not particularly limited, but is preferably lower than that of the crystalline alkali metal silicate (component (A)) not subjected to the treatment of the present invention. It is more preferable that the value be lower by 5 or more, and further more preferable that the value be 1.0 or lower. The weight increase rate and the amount of acicular crystals produced can be measured according to the methods described in Examples below.

5. Detergent Composition The crystalline alkali metal silicate treated by the treatment method of the present invention is a water-soluble ion exchanger and also has an alkali buffering ability and has improved caking resistance. Therefore, it is suitably used as a detergent builder. When used as a detergent builder, the crystalline alkali metal silicate may be granulated in advance and added to the detergent, or the crystalline alkali metal silicate may be mixed with other detergent formulations as required. Detergent particles may be formed. Moreover, although it is preferable to process all the crystalline alkali metal silicate contained in a detergent composition by the processing method of this invention, you may contain the crystalline alkali metal silicate which does not process. In this case, the amount of the crystalline alkali metal silicate of the present invention is preferably 50% by weight or more, more preferably 60% by weight or more in the total crystalline alkali metal silicate.

  The content of the crystalline alkali metal silicate in the detergent composition of the present invention is not particularly limited, but is preferably 1% by weight or more of the detergent composition in order to develop effective builder performance. In order to adjust the pH of the product to an appropriate range, it is preferably 50% by weight or less. The content of the crystalline alkali metal silicate is preferably 1 to 50% by weight and more preferably 2 to 25% by weight in the detergent composition of the present invention.

  The detergent composition of the present invention can contain a surfactant, a water-soluble polymer, a water-soluble salt, a water-insoluble substance and the like in addition to the crystalline alkali metal silicate.

  The surfactant that can be used in the detergent composition of the present invention is, for example, selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. One or more types can be used. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester thereof, alkyl or alkenyl ether carboxylate, amino acid type surfactant And N-acylamino acid type surfactants. In particular, linear alkylbenzene sulfonate having 10 to 14 carbon atoms, alkyl sulfate or alkyl ether sulfate having 10 to 18 carbon atoms, and examples of the base include alkali metals such as sodium and potassium, monoethanolamine, diethanolamine and the like. Are preferred.

  Furthermore, in order to obtain an antifoaming effect, a fatty acid salt can be used in combination. The carbon number of a preferable fatty acid is 12-18.

Examples of the nonionic surfactant include polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl or alkenyl phenyl ether, polyoxyethylene polyoxypropylene alkyl or alkenyl ether, and polyoxyethylene polyoxypropylene glycol represented by trademark Pluronic , Polyoxyethylene alkylamine, higher fatty acid alkanolamide, alkyl glucoside, alkyl glucose amide, alkyl amine oxide and the like. Among them, those having high hydrophilicity and those having a low liquid crystal forming ability when mixed with water or those that do not produce liquid crystal are preferable, and polyoxyalkylene alkyl or alkenyl ether is particularly preferable. Preferably, the alcohol ethylene has 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and an average added mole number of 5 to 30, preferably 7 to 30, more preferably 9 to 30 and more preferably 11 to 30. An oxide (hereinafter referred to as EO) adduct, an EO adduct of alcohol having 8 to 18 carbon atoms, and a propylene oxide (hereinafter referred to as PO) adduct are preferable. As the addition order, one added with PO after adding EO, one added with PO after adding PO, or one added randomly with EO and PO can be used. Is a general formula in which EO is added, PO is added as a block, and EO is added as a block:
R-O- (EO) _X- (PO) _Y- (EO) _Z- H
[In the formula, R represents a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group or an alkenyl group, EO represents an oxyethylene group, PO represents an oxypropylene group, and X, Y, and Z each represent an average addition mole number. ]
Among these, the most preferable average added mole number relationship is X> 0, Z> 0, X + Y + Z = 6 to 14, X + Z = 5 to 12, Y = 1 to 4 It is.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.

  Examples of amphoteric surfactants include carbobetaine type and sulfobetaine type.

  The content of the surfactant in the detergent composition is preferably 5 to 60% by weight and more preferably 15 to 50% by weight from the viewpoints of detergency and rinsing properties.

  Examples of the water-soluble polymer contained in the detergent composition of the present invention as a chelating agent or a dispersant include carboxylic acid polymers, cellulose derivatives such as carboxymethyl cellulose, aminocarboxylic acids such as polyglyoxylate and polyaspartate. One or more selected from the group consisting of a polymer, a soluble starch, a saccharide, etc. can be exemplified as a preferable one. Among them, a carboxylic acid polymer is a finer action of water-soluble salts, and a detergency, specifically, a metal It is more preferable from the viewpoint of the action of sequestering ions, the action of dispersing solid particle dirt from the garment into the washing bath, and the action of preventing the particles from reattaching to the garment.

Among the carboxylic acid-based polymers, acrylic acid-maleic acid copolymers and their salts (Na, K, NH ₄ etc.) and acrylic acid polymers and their salts (Na, K, NH ₄ etc.) are particularly excellent.

  The weight average molecular weight of these water-soluble polymers is preferably from 1,000 to 300,000, more preferably from 2,000 to 100,000, further preferably from 2,000 to 80,000, particularly preferably from 5,000 to 50,000, and from 6,000 to 20,000. Is particularly preferred.

As molecular weight measurement method,
1. Conversion standard material: Polyacrylic acid (AMERICAN STANDARDS CORP)
2. Eluent: 0.2 mol / L phosphate buffer / CH ₃ CN: 9/1 (volume ratio)
3. Column: PWXL + G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
4). Detector: RI
5. Sample concentration: 5 mg / mL
6). Injection volume: 0.1 mL
7). Measurement temperature: 40 ° C
8). Flow rate: 1.0 mL / min
To do.

  In addition to the above carboxylic acid polymers, polymers such as polyglyoxylate, cellulose derivatives such as carboxymethylcellulose, and aminocarboxylic acid polymers such as polyaspartate also have sequestering ability, dispersibility and recontamination prevention ability. It can be used as having.

  Other examples include polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polypropylene glycol (PPG), etc. PVP is preferred as a color transfer inhibitor, and PEG and PPG having a molecular weight of about 1,000 to 20,000 are powder detergents. Is preferable because it improves the paste viscosity characteristics produced when water is contained.

  The content of the water-soluble polymer in the detergent composition is preferably 1.5 to 25% by weight, more preferably 2 to 22.5% by weight, still more preferably 2.5 to 20% by weight, and 3 to 17.5% by weight. % Is particularly preferable, and 3.5 to 15% by weight is most preferable. Within this range, the strength of the detergent granules is sufficiently high.

  In the detergent composition of the present invention, the water-soluble salts used as an alkaline buffer and a filler are preferably those described below. Examples of the water-soluble salts include water-soluble inorganic salts such as carbonic acid, sulfuric acid, hydrogen carbonate, sulfurous acid, hydrogen sulfate, and phosphoric acid (for example, alkali metal salts, ammonium salts, or amine salts). Moreover, halogenated alkali metal salts (for example, sodium salt or potassium salt) and alkaline earth metal salts (for example, calcium salt or magnesium salt) such as chloride, bromide, iodide, and fluoride can be used.

  Of these, carbonates, sulfates and sulfites are preferred. Carbonate is preferable as an alkaline agent exhibiting a suitable pH buffer region in the washing liquid, and salts having a high degree of dissociation such as sulfate and sulfite increase the ionic strength of the washing liquid and act suitably for cleaning sebum dirt. . Sulphite has the effect of reducing hypochlorite ions contained in tap water and preventing oxidative deterioration due to hypochlorite ions of detergent components such as enzymes and perfumes. Sodium tripolyphosphate can also be used as a water-soluble salt.

  The water-soluble salt may be composed of a single component or a combination of a plurality of components such as carbonate and sulfate.

  Examples of the low molecular weight water-soluble organic acid salts include carboxylic acid salts such as citrate and fumarate. From the viewpoint of detergency, methyliminodiacetate, iminodisuccinate, ethylenediaminedisuccinate, taurine diacetate, hydroxyethyliminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate Preferred examples include salts, glutamic acid diacetate, asparagine diacetate, serine diacetate and the like.

  The content of the water-soluble salt in the detergent composition is preferably 5 to 45% by weight, more preferably 7.5 to 42.5% by weight, still more preferably 10 to 37.5% by weight, and 12.5 to 35%. % By weight is particularly preferred and 15 to 35% by weight is most preferred. If it is in these ranges, the particle strength of the detergent particles will be sufficiently high, and the solubility of the detergent particles is also preferred.

  In the detergent composition of the present invention, for example, a water-insoluble substance such as zeolite is preferably contained in terms of detergency because it has a sequestering ability. As such a water-insoluble substance, crystalline aluminosilicate, amorphous aluminosilicate, silicon dioxide, hydrated silicate compound, clay compound such as perlite, bentonite, etc. can be used. preferable. Moreover, 0.1-10 micrometers is preferable and, as for the average particle diameter of this aluminosilicate, 0.5-5 micrometers is more preferable.

  Suitable as the crystalline aluminosilicate is A-type zeolite (for example, trade name: “Toyo Builder”; manufactured by Tosoh Corporation, trade name: “synthetic zeolite”; manufactured by Nippon Builder Co., Ltd., trade name: “ VALFOR100 ”“ VALFOR300 ”; PQ CHEMICALS (Thailand) Ltd., trade name:“ ZEOBUILDER ”; ZEOBILDER Ltd; trade name:“ VEGOBOND A ”; From the viewpoint of sequestering ability and economy. Here, it is preferable that the value of the supporting ability of A-type zeolite according to JIS K 5101 method is 40 to 50 mL / 100 g. In addition, P type (for example, trade names “Ducil A24”, “ZSE064”, etc .; manufactured by Crosfield; carrying capacity 60 to 150 mL / 100 g) and X type (for example, trade name: “WesalithXD”; manufactured by Degussa; carrying capacity 80 to 80 100 mL / 100 g). The hybrid zeolite described in WO9842622 is also a suitable crystalline aluminosilicate.

  Moreover, amorphous aluminosilicate, amorphous silica, etc. which have a low metal ion sequestering ability but a high carrying ability can also be contained in the detergent composition. For example, Japanese Patent Application Laid-Open No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (particularly, the initial temperature is preferably in the range of 15 to 60 ° C.), Japanese Patent Application Laid-Open No. 62-191419. Amorphous aluminosilicate described in the second page, lower right column, line 20 to page 5, lower left column, line 11 (particularly, the oil absorption is preferably 170 mL / 100 g), and JP-A-9-132794. Column 17, line 46 to column 18, line 38, JP-A-7-10526, column 3, line 3 to column 5, line 9, JP-A-6-227811, column 2, line 15 to 5 Examples include amorphous aluminosilicate (supporting capacity 285 mL / 100 g) described in column 2, line 2, JP-A-8-119622, column 2, line 18 to column 3, line 47, and the like. For example, “Toceal NR” (manufactured by Tokuyama Soda Co., Ltd .: carrying capacity 210-270 mL / 100 g), “FLORITE” (same as above: carrying capacity 400-600 mL / 100 g), “TIXOLEX25” (manufactured by Han France Chemical Co., Ltd .: An oil-absorbing carrier such as “support capacity 220-270 mL / 100 g” and “Silo Pure” (manufactured by Fuji Divison Co., Ltd .: support capacity 240-280 mL / 100 g) can be used. As the oil absorbing carrier, those described in JP-A-6-179899, column 12, line 12 to column 13, line 1 and column 17, line 34 to column 19, line 17 are suitable.

  The content of the water-insoluble substance in the detergent composition is preferably 0 to 65% by weight, more preferably 5 to 60% by weight, still more preferably 10 to 55% by weight, particularly preferably 15 to 50% by weight, 20 -45 wt% is most preferred. Within this range, a detergent composition having high cleaning performance and excellent particle strength and solubility can be obtained.

  The water-insoluble substance may be composed of a single component or a plurality of components.

  The detergent composition may contain auxiliary components such as known fluorescent dyes, pigments, dyes, enzymes and the like. The content of the auxiliary component is preferably 15% by weight or less in the detergent composition, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

6). Manufacturing method of detergent composition The detergent composition of the present invention is characterized by excellent resistance to caking in the form of powder and granules. However, the form is not particularly limited and may take the form of a tablet, a paste, or the like. Also, the production method is not particularly limited, and blending is possible only with powder raw materials including crystalline alkali metal silicate. When liquid raw materials are included, operations such as drying are performed in addition to blending. You may use together. Below, the manufacturing method in the case of making it granular is shown as an example.

Step (a): preparing a slurry containing a water-soluble polymer, a water-insoluble substance and a water-soluble salt,
Step (b): Spray drying the slurry to prepare a surfactant-supporting granule group,
Step (c): Under conditions where the surfactant composition is in a liquid state, the surfactant-supporting granules obtained in step (b), the surfactant composition, and the crystalline alkali metal silicate of the present invention are used. Mixing,
Step (d): It comprises a step of mixing the mixture obtained in step (c) with fine powder and coating the surface of the detergent particles with the fine powder. Hereinafter, each process will be described in detail.

<Process (a)>
The slurry prepared in the step (a) may be a non-curable slurry that can be pumped. If the temperature of the slurry becomes too high or too low, the solubility of the water-soluble salts will decrease, and the viscosity of the slurry will increase, which is not preferable in terms of pumpability. That is, the slurry temperature is preferably 30 to 80 ° C, more preferably 35 to 65 ° C.

  Further, the smaller the water content of the slurry, the less the water evaporated in the drying process, which is preferable in terms of productivity. The more the slurry water is, the more water-soluble salts are dissolved and the lower the slurry viscosity, the more preferable in terms of pumping properties. Accordingly, the slurry moisture is preferably 30 to 70% by weight, more preferably 35 to 65% by weight, and most preferably 40 to 60% by weight.

  As a slurry preparation method, the addition method and order of components can be appropriately changed depending on the situation. For example, all or almost all of the water is first added to the mixing vessel, preferably after the water temperature has nearly reached the set temperature, the other ingredients are added sequentially or simultaneously. As a normal order of addition, a liquid component such as polyacrylate is added first, and then a water-soluble powder raw material such as soda ash is added. A small amount of auxiliary components such as dyes are also added. Finally, a water-insoluble component such as a water-insoluble substance such as zeolite is added. At that time, for the purpose of improving the mixing efficiency, the water-insoluble component may be added in two or more portions. Moreover, you may add a powder raw material in an aqueous medium after mixing previously. Further, water may be added to adjust viscosity and slurry moisture after all components are added. In order to finally obtain a homogeneous slurry, after all components are added to the slurry, it is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

<Step (b)>
As a method for drying the slurry, spray drying in which the particle shape is substantially spherical is particularly preferable. As the spray-drying tower, a countercurrent tower is more preferable because thermal efficiency and particle strength of the surfactant-supporting granules are improved. The slurry atomizer may be any of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but a pressure spray nozzle is particularly preferable in order to obtain a desired average particle size.

  By adjusting the temperature of the gas supplied to the drying tower and the amount of gas blown, the water content of the obtained granules for supporting a surfactant can be adjusted. Considering productivity, ease of production and safety, the temperature of the gas supplied to the drying tower is 140 to 360 ° C, preferably 170 to 330 ° C. Moreover, the temperature of the gas discharged | emitted from a drying tower is 70-105 degreeC at the point of the thermal efficiency of a drying tower, Preferably it is 75-100 degreeC. Further, the particles for supporting a surfactant after spray drying may be further dried by an air dryer, a fluidized bed dryer, a rotary dryer or the like.

<Step (c)>
The amount of the surfactant to be supported on the surfactant-carrying granule group used in the present invention is preferably 5 to 80 parts by weight with respect to 100 parts by weight of the surfactant-carrying granule group from the viewpoint of exerting detergency. 5 to 60 parts by weight is more preferable, 10 to 60 parts by weight is further preferable, and 20 to 60 parts by weight is particularly preferable. Here, the loading amount of the anionic surfactant is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, and particularly preferably 3 to 40 parts by weight. The amount of the nonionic surfactant supported is preferably 1 to 45 parts by weight, more preferably 1 to 35 parts by weight, and still more preferably 4 to 25 parts by weight. The nonionic surfactant can be used alone, but is preferably mixed with an anionic surfactant. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose. The loading amount of the surfactant referred to here does not include the addition amount of the surfactant when the surfactant is added during the slurry preparation in the step (a).

  As a method for supporting the surfactant on the surfactant-supporting granule group, for example, a batch-wise or continuous known mixer can be used. Moreover, when performing by a batch type, the preparation method to a mixer is as follows. (1) After supplying the granule group for surfactant support to a mixer first, surfactant is added. (2) Charge the surfactant-supporting granule group and the surfactant into the mixer little by little. (3) After a part of the surfactant-carrying granule group is charged into the mixer, the remaining surfactant-carrying granule group and the surfactant are charged in small amounts. Etc. can be taken. In addition, the method of (1)-(3) is performed, operating a mixer.

  Among these methods, the above (1) is particularly preferable. The surfactant is preferably added in a liquid state, and it is preferable to spray and supply a surfactant in the liquid state.

  Among the surfactants, those that exist in a solid or paste form even if the temperature is raised within a practical temperature range, such as a nonionic surfactant or a nonionic surfactant having a low viscosity in advance. A surfactant mixed solution or aqueous solution can be prepared by dispersing or dissolving in an aqueous solution or water, and added to the surfactant-supporting granules in the form of the mixed solution or aqueous solution. By this method, a surfactant present in a solid or paste form can be easily added to the surfactant-supporting granules, and it is advantageous for producing detergent particles containing mononuclear detergent particles. . The mixing ratio of the low-viscosity surfactant or water and the solid or pasty surfactant is preferably within a viscosity range in which the resulting mixed solution or aqueous solution can be sprayed. For example, polyoxyethylene dodecyl ether and dodecyl benzene sulfone. If it is sodium acid, the surfactant liquid mixture which can be easily sprayed can be obtained by adjusting the weight ratio of both in the range of 1: 1.4-1.4: 1.

  Examples of the method for producing the above mixed liquid include a method in which a surfactant having a low viscosity or a surfactant in the form of a solid or paste is added to water and mixing, or a surfactant acid in a low viscosity surfactant or in water. A surfactant mixed solution may be prepared by neutralizing the precursor with an alkali agent (for example, an aqueous caustic soda solution or an aqueous caustic potash solution).

  Examples of the acid precursor of the anionic surfactant that can be used in the present invention include alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefin sulfonic acid, α-sulfonated fatty acid, and alkyl. Or an alkenyl ether carboxylic acid, a fatty acid, etc. are mentioned. In particular, it is preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.

  The amount of the acid precursor of the anionic surfactant used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the surfactant-supporting granule group. The amount of the anionic surfactant acid precursor used in this range tends to maintain the mononuclearity of the particles in the detergent particles, and thus exhibits good fast solubility. In addition, as a method for adding the acid precursor of the anionic surfactant, it is preferable to spray and supply a liquid at room temperature, and a solid at room temperature may be added as a powder or melted. You may supply after spraying. However, when adding with a powder, it is preferable to raise the temperature of the detergent particle group in a mixer to the temperature which a powder fuse | melts.

  As an apparatus preferably used in the step (c), Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Paulek Co., Ltd.), Redige There are mixers (manufactured by Matsuzaka Giken Co., Ltd.), pro-shear mixers (manufactured by Taiheiyo Kiko Co., Ltd.), and nauter mixers (manufactured by Hosokawa Micron Co., Ltd.).

  As a preferable mixer, from the viewpoint of producing a detergent particle group containing a large amount of mononuclear detergent particles, an apparatus in which a strong shearing force is not easily applied to the surfactant-carrying granules (the surfactant-carrying granules are not easily disintegrated) is used. In view of the dispersion efficiency of the surfactant, an apparatus having good mixing efficiency is preferable. Among the mixers described above, it is particularly preferable that a horizontal mixing tank has a stirring shaft at the center of a cylinder, and a mixer (horizontal mixer) of a type in which a stirring blade is attached to this shaft to mix powder is ready. There are mixers and professional share mixers.

  Further, the surfactant may be supported on the surfactant-supporting granule group using the continuous device of the mixer. In addition, examples of the continuous apparatus other than the above include a flexo-mix type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.), and the like.

  In this step, when a nonionic surfactant is used, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1000 to 30000 (hereinafter referred to as a melting point) is used as a melting point raising agent for the surfactant. It is also possible to add this aqueous solution before addition of the surfactant, simultaneously with the addition of the surfactant, during the addition of the surfactant, after the addition of the surfactant, or mixed in advance with the surfactant. Is possible. By adding a melting point increasing agent, it is possible to suppress the bleed-out property of the surfactant in the detergent particle group. Examples of the melting point raising agent that can be used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic-type nonionic surfactant.

  The amount of the melting point raising agent used is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the surfactant-supporting granule group. This range is preferable from the viewpoints of maintaining mononuclearity of the detergent particles contained in the detergent particle group, high-speed solubility, and suppression of smearing. As a method for adding the melting point increasing agent, it is advantageous to prevent the detergent particle group from smearing by adding the surfactant in advance by mixing with a surfactant or adding a melting point increasing agent after adding the surfactant. is there.

  It is more preferable that the temperature in the mixer is increased to the melting point of the surfactant or higher for mixing. Here, the temperature to be raised may be higher than the melting point of the surfactant to be added to promote the loading of the surfactant, but in a practical range, the temperature exceeds the melting point and is 50 ° C. higher than the melting point. Up to 10 ° C. to 30 ° C. higher than the melting point is more preferable. Moreover, when adding the acid precursor of an anionic surfactant at this process, it is more preferable if it heats up to the temperature which can react the acid precursor of the said anionic surfactant, and it mixes.

  The batch mixing time for obtaining a suitable detergent particle group and the average residence time in continuous mixing are preferably 1 to 20 minutes, more preferably 2 to 10 minutes.

  In the step (c), the crystalline alkali metal silicate of the present invention may be added before the addition of the surfactant, simultaneously with the addition of the surfactant, during the addition of the surfactant, or after the addition of the surfactant. Is possible. The crystalline alkali metal silicate of the present invention is preferably added in this step (c), but a part thereof may be added in step (d) as a surface modifier, or the crystalline alkali metal silicate. After blending may be performed as granules.

  When the crystalline alkali metal silicate of the present invention is added, before the addition, simultaneously with the addition, during the addition, after the addition, the powder builder other than the crystalline alkali metal silicate of the present invention, and / or the interface of the powder It is also possible to add activators. By adding a powder builder, the particle diameter of the detergent particles can be controlled, and the cleaning power can be improved. In particular, when an acid precursor of an anionic surfactant is added, it is effective from the viewpoint of accelerating the neutralization reaction to add an alkaline powder builder before adding the acid precursor. In addition, the powder builder said here means a detergency enhancing agent for powders other than the surfactant, and specifically, a base that exhibits sequestering ability such as zeolite and citrate, sodium carbonate, It refers to a base that exhibits alkaline ability such as potassium carbonate, and a base that enhances ionic strength such as sodium sulfate. Moreover, you may add the alkali metal silicate which has not performed the process of this invention.

  As the usage-amount of the said powder builder, 0.5-12 weight part is preferable with respect to 100 weight part of granule groups for surfactant carrying | support, and 1-6 weight part is further more preferable. The amount of the detergent powder builder used is within this range, the mononuclearity of the detergent particles contained in the detergent particle group is maintained, good high-speed solubility can be obtained, and control of the particle diameter is also suitable.

<Step (d)>
In the present invention, in order to modify the particle surface of the detergent particle group carrying the surfactant in the step (c), the form at the time of addition is as follows: Such a surface modification step for adding various surface coating agents may be performed in one step or two steps.

  When the surface of the detergent particle group is coated, the flowability and caking resistance of the detergent particle group tend to be improved. Therefore, it is preferable to perform the step (c) which is a surface modification step. The apparatus used in the surface modification step is not particularly limited, and a known mixer can be used, but the mixer exemplified in the above step (c) is preferable. Each of the surface modifiers will be described below.

  The surface modifier preferably has an average primary particle size of 10 μm or less, more preferably 0.1 to 10 μm. When the average particle size is within this range, the coverage of the detergent particle group on the particle surface is improved, which is preferable from the viewpoint of improving the fluidity and caking resistance of the detergent particle group. The average particle diameter of the fine powder is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.), or measurement of a ferret diameter by SEM. Moreover, it is preferable from a washing | cleaning surface that this fine powder has a high ion exchange ability and a high alkali ability.

  The fine powder is particularly preferably an aluminosilicate, which may be crystalline or amorphous. Other than the aluminosilicate, fine powders such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, and amorphous silica derivatives are also preferable. A crystalline alkali metal silicate subjected to the treatment of the present invention and having an average particle size of 10 μm or less can be used as a surface modifier. Further, a metal soap having primary particles of 0.1 to 10 μm, a powdery surfactant (for example, alkyl sulfate) and a water-soluble organic acid salt can be used in the same manner.

  The amount of the fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 20 parts by weight with respect to 100 parts by weight of the detergent particle group. When the amount of the fine powder used is within this range, the fluidity is improved and the consumer feels good.

  Moreover, it is also possible to add another washing | cleaning component to the detergent particle group obtained through the process (d). As the separately added detergent component, for example, a granulated product of the crystalline alkali metal silicate of the present invention, a fluorescent dye, an enzyme, a fragrance, an antifoaming agent, a bleaching agent, a bleaching activator and the like are preferable.

  The content of the detergent particles in the detergent composition is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, and particularly preferably 80% by weight or more from the viewpoint of detergency.

  The content of detergent components other than the detergent particle group in the detergent composition is preferably 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less, and particularly preferably 20% by weight or less.

  The crystalline alkali metal silicate of the present invention can be suitably used as a raw material for a detergent composition. When producing the detergent composition, the surfactant-supporting granule group obtained in the step (b) without performing the step (c) and the crystalline alkali metal silicate of the present invention are mixed together with the surfactant, Consolidation and granulation treatment may be performed, and the method is not particularly limited to the method of impregnating the surfactant as in step (c).

  Although it does not specifically limit as a use of the detergent composition of this invention, Especially, it uses suitably as a detergent for clothes.

Although the processing method of the crystalline alkali metal silicate of this invention is illustrated below, the processing method of the crystalline alkali metal silicate of this invention is not limited to this. In Examples and Comparative Examples, the physical properties of crystalline alkali metal silicates were evaluated by the following test methods.
(Weight increase rate): 1.0 g of crystalline alkali metal silicate is weighed in a petri dish and stored for 14 days in an environment of temperature 20 ° C. and humidity 65% RH, or in an environment of temperature 30 ° C. and humidity 70% RH. The weight increase rate was calculated by the following method.
Weight increase rate (%) = 100 × (ab) / b
a: Weight after storage (g)
b: Weight before storage (g)
(Acicular crystal production amount): After storing the crystalline alkali metal silicate in an environment of 20 ° C. and 65% RH for 28 days, a powder X-ray diffractometer (manufactured by Rigaku Corporation, “RINT2000”) The X-ray diffraction pattern was measured. Among the obtained diffraction patterns, the amount of acicular crystals formed was calculated by the following formula using the values before and after storage for the peak intensity of sodium sesquicarbonate appearing near the lattice constant d = 9.77.
Acicular crystal production amount = p / q
p: peak intensity after storage q: peak intensity before storage

In this example, the following raw materials were used unless otherwise specified.
Crystalline layered sodium disilicate: “Prefeed N” (manufactured by Tokuyama Siltech Co., Ltd.)
Sodium sulfate: “Anhydrous neutral sodium sulfate” (manufactured by Shikoku Kasei Co., Ltd.)
Sodium sulfite: “Soda sulfite” (Mitsui Chemicals, Inc.)
Fluorescent dye: “Chino Pearl CBS-X” (manufactured by Ciba Specialty Chemicals)
Sodium carbonate: “Dense ash” (average particle size: 290 μm, manufactured by Central Glass Co., Ltd.)
40% by weight sodium polyacrylate aqueous solution: weight average molecular weight 10,000 (manufactured by Kao Corporation)
Sodium chloride: “Baked salt S” (manufactured by Nippon Salt Corporation)
Zeolite: “Toyo Builder” (4A type, average particle size: 3.5 μm), manufactured by Tosoh Corporation
Sodium alkylbenzene sulfonate: "Neopelex GS" (alkylbenzenesulfonic acid non-neutralized product, manufactured by Kao Corporation) neutralized with 48% NaOH Polyoxyethylene alkyl ether: "Emulgen 108KM" (ethylene oxide average addition) Number of moles: 8.5, carbon number of alkyl chain: 12-14, manufactured by Kao Corporation)
Polyethylene glycol: “K-PEG6000” (weight average molecular weight: 8500, manufactured by Kao Corporation)

Example 1
・ Pulverization of crystalline layered sodium disilicate granules Crystalline layered sodium disilicate granules ("Prefeed N", Tokuyama Siltec Co., Ltd., center particle size (d50) 682 μm, no binder) are used in a vertical roller mill. , mill rotation speed 43r / min, So圧80 mm, mill inlet pressure 150MmAq, mill outlet pressure -170MmAq, bag filter differential pressure 170MmAq, rolling pressure 25 kg / cm ^2, the separator rpm 550R / min, separator current 4.1A, the raw material It grind | pulverized on the conditions of a supply rate of 15 kg / hr. The average particle size of the obtained crystalline sodium silicate pulverized product was 6.6 μm.
The composition of the crystalline sodium silicate was Na ₂ O.2SiO ₂ .

-Mixing of crystalline alkali metal silicate and component (B) 475 g of crystalline sodium silicate pulverized product was added to a 9 L Henschel mixer (Mitsui Miike Koki Co., Ltd. "FM10B"). While the jacket temperature was 20 ° C., 25 g of tap water was added with a dropper over 60 seconds while stirring at 3500 r / min. Thereafter, the mixture was stirred at 3500 r / min for 120 seconds to produce crystalline alkali metal silicate (after treatment) 1. The average particle size of the obtained crystalline alkali metal silicate (after treatment) 1 was 8.0 μm. Also, (after treatment) 1 of the composition of the crystalline sodium silicate was _{Na 2 O · 2SiO 2 · 1.6H} 2 O.

-Physical Properties of Crystalline Alkali Metal Silicate (After Treatment) A part of the obtained crystalline alkali metal silicate (after treatment) 1 has a weight increase rate of 12.degree. It was 5%. In addition, the weight increase rate of crystalline alkali metal silicate (after treatment) 1 after storage at 30 ° C., 70% RH for 14 days was 14.4%. Crystalline alkali metal silicate (after treatment) 1 had a needle crystal production of 2.9 after storage at 20 ° C., 65% RH, 28 days.

Example 2
Crystalline alkali metal silicate (after treatment) 2 was produced under the same conditions as in Example 1 except that the addition amount of the crystalline sodium silicate pulverized product was changed to 485 g and the addition amount of tap water was changed to 15 g. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 2 was 7.3 μm. The composition of this crystalline sodium silicate (after treatment) 2 was Na ₂ O.2SiO ₂ .H ₂ O. Part of the obtained crystalline alkali metal silicate (after treatment) 2 had a weight increase rate of 13.5% after storage at 20 ° C. and 65% RH for 14 days. The weight increase rate of crystalline alkali metal silicate (after treatment) 2 after storage at 30 ° C., 70% RH for 14 days was 16.6%. Crystalline alkali metal silicate (after treatment) 2 had an acicular crystal production of 3.5 after storage at 20 ° C. and 65% RH for 28 days.

Example 3
Crystalline alkali metal silicate (after treatment) 3 was produced under the same conditions as in Example 1 except that the addition amount of the crystalline sodium silicate pulverized product was changed to 495 g and the addition amount of tap water was changed to 5 g. The average particle size of the obtained crystalline alkali metal silicate (after treatment) 3 was 6.9 μm. The composition of this crystalline sodium silicate (after treatment) 3 was Na ₂ O.2SiO ₂ .0.3H ₂ O. A part of the obtained crystalline alkali metal silicate (after treatment) 3 had a weight increase rate of 14.1% after storage at 20 ° C. and 65% RH for 14 days. The weight increase rate of crystalline alkali metal silicate (after treatment) 3 after storage at 30 ° C., 70% RH for 14 days was 18.5%. The amount of acicular crystals formed after crystalline alkali metal silicate (after treatment) 3 was stored at 20 ° C., 65% RH, 28 days was 4.0.

Example 4
Lithium sulfate monohydrate (special reagent grade, manufactured by Sigma-Aldrich Japan) 23.28 g was dissolved in 76.8 g of tap water to prepare a 20 wt% lithium sulfate aqueous solution. Crystalline alkali metal silicate (after treatment) under the same conditions as in Example 1 except that the amount of crystalline sodium silicate pulverized product was changed to 485 g and 15 g of 20 wt% aqueous lithium sulfate was added instead of tap water. 4 was produced. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 4 was 7.5 μm. The composition of the crystalline sodium silicate (after treatment) 4 was _{Na 2 O · 2SiO 2 · 0.8H} 2 O. A part of the obtained crystalline alkali metal silicate (after treatment) 4 had a weight increase rate of 11.5% after storage at 20 ° C. and 65% RH for 14 days. The weight increase rate of crystalline alkali metal silicate (after treatment) 4 after storage at 30 ° C., 70% RH for 14 days was 16.0%. The amount of acicular crystals formed after crystalline alkali metal silicate (after treatment) 4 was stored at 20 ° C. and 65% RH for 28 days was 3.4.

Example 5
The addition amount of the crystalline sodium silicate pulverized product was changed to 485 g, and lithium silicate (manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ : 21.6%, Li ₂ O: 2.8%, molar ratio instead of tap water) A crystalline alkali metal silicate (after treatment) 5 was produced under the same conditions as in Example 1 except that 15 g of 3.79) was added. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 5 was 7.5 μm. The composition of the crystalline sodium silicate (after treatment) 5 was _{Na 2 O · 2SiO 2 · 0.7H} 2 O. A part of the obtained crystalline alkali metal silicate (after treatment) 5 had a weight increase rate of 13.1% after storage at 20 ° C., 65% RH for 14 days. The weight increase rate of crystalline alkali metal silicate (after treatment) 5 after storage at 30 ° C., 70% RH for 14 days was 17.2%. Crystalline alkali metal silicate (after treatment) 5 had an acicular crystal production of 4.3 after storage at 20 ° C. and 65% RH for 28 days.

Comparative Example 1
A crystalline alkali metal silicate (after treatment) 6 was produced under the same conditions as in Example 1 except that the amount of the crystalline sodium silicate pulverized product was changed to 500 g and no other additives were added. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 6 was 6.6 μm. The composition of this crystalline sodium silicate (after treatment) 6 was Na ₂ O · 2SiO ₂ . A part of the obtained crystalline alkali metal silicate (after treatment) 6 had a weight increase rate of 15.0% after storage at 20 ° C. and 65% RH for 14 days. The weight increase rate of the crystalline alkali metal silicate (after treatment) 6 after storage at 30 ° C., 70% RH for 14 days was 18.8%. Crystalline alkali metal silicate (after treatment) 6 had an acicular crystal production of 5.3 after storage at 20 ° C. and 65% RH for 28 days.

Comparative Example 2
20 g of lithium sulfate monohydrate (reagent special grade: manufactured by Sigma-Aldrich Japan) was added to an agate mill made of agate and ground at 8000 r / min for 5 minutes to obtain a ground product of lithium sulfate monohydrate. The amount of the crystalline sodium silicate pulverized product was changed to 485 g, and the crystalline alkali metal silicate (under the same conditions as in Example 1 except that 15 g of the lithium sulfate monohydrate pulverized product was added instead of tap water. 7) was produced after treatment. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 7 was 6.8 μm. The composition of the crystalline sodium silicate (after treatment) 7 was a Na ₂ O · 2SiO _2. Part of the obtained crystalline alkali metal silicate (after treatment) 7 had a weight increase rate of 14.8% after storage at 20 ° C. and 65% RH for 14 days. The weight increase rate of crystalline alkali metal silicate (after treatment) 7 after storage at 30 ° C., 70% RH for 14 days was 18.9%. Crystalline alkali metal silicate (after treatment) 7 had a needle crystal production of 5.1 after storage at 20 ° C., 65% RH, 28 days.

Comparative Example 3
A crystalline alkali metal silicate (after treatment) 8 was produced under the same conditions as in Example 1 except that the addition amount of the crystalline sodium silicate pulverized product was changed to 375 g and the addition amount of tap water was changed to 125 g. The average particle diameter of the obtained crystalline alkali metal silicate (after treatment) 8 was 18.3 μm. The composition of the crystalline sodium silicate (after treatment) 8 was _{Na 2 O · 2SiO 2 · 10.2H} 2 O. Part of the obtained crystalline alkali metal silicate (after treatment) 8 had a weight increase rate of 8.5% after storage at 20 ° C., 65% RH for 14 days. The weight increase after storage for 14 days at 30 ° C. and 70% RH was 10.3%. The amount of acicular crystals produced after storage at 20 ° C. and 65% RH for 28 days was 3.1.

  Tables 1 and 2 summarize the composition and physical property evaluation results of the obtained crystalline alkali metal silicate (after treatment). Since the crystalline alkali metal silicates (after treatment) 1 to 5 obtained in Examples 1 to 5 are intimately mixed with the crystalline layered sodium disilicate and the component (B), in Comparative Examples 1 and 2 Compared to the obtained crystalline alkali metal silicate (after treatment) 6 to 7, the weight increase rate due to storage is low, and the amount of acicular crystals produced is also suppressed to a low level. The crystalline alkali metal silicate (after treatment) 6 of Comparative Example 1 has no additive, and the crystalline alkali metal silicate (after treatment) 7 of Comparative Example 2 has the addition of water as an essential component of (B). Not done. The crystalline alkali metal silicate (after treatment) 8 of Comparative Example 3 has a large amount of the component (B) added, has a low weight increase rate, and is suppressed to a low level of acicular crystals. However, the component (B) acts as a binder, and the degree of particle growth is large and the average particle size is large, which is not preferable in terms of solubility and cleaning performance.

  Next, using the obtained crystalline alkali metal silicate (after treatment) 1 to 8, a detergent composition was prepared as follows. In addition, the physical property of the obtained detergent composition was evaluated with the following test methods.

(Moisture): Measured by the method defined by JIS K 0068.

(Average particle diameter): After oscillating for 5 minutes using a standard sieve of JIS Z 8801 (mesh opening 2000 to 125 μm), the median diameter is calculated from the weight fraction depending on the size of the sieve mesh.

(Bulk density): Measured by a method defined by JIS K 3362.

(Flowability): The flow time is the time required for 100 mL of the powder to flow out from the bulk density measurement hopper specified by JIS K 3362.

(Caking resistance): length × width × height = 14.5 cm × 9.2 cm × using two types of filter papers defined in JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Roshi Kaisha, Ltd.) Make a container with an open top of 13.5 cm. Place 1200 g of detergent particle group sample in this box. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 70%, and the caking state is determined after 8 days. The determination is made by gently opening the sample after the test on a sieve (4760 μm opening according to JIS Z 8801), measuring the weight of the passed powder, and determining the passage rate for the sample after the test. The higher the pass rate, the higher the caking resistance, which is a preferable physical property as a detergent particle group.

(Ca ion exchange capacity) of the sample 0.04g accurately weighed, calcium chloride solution (concentration 100ppm as CaCO ₃₎ was added into 100 mL, and stirred for 10 minutes at 20 ° C.. Thereafter, the obtained liquid was filtered with a 0.2 μm filter, and the amount of Ca contained in 10 mL of the filtrate (CaCO ₃ equivalent amount) was quantified by EDTA titration. The Ca ion exchange capacity was calculated | required from the value.

(Cleaning performance): Performed by the method described in JP-A-9-241697, column 16, line 1 to line 42.

Example 6
486 parts by weight of water was added to the mixing tank, and after the water temperature reached 45 ° C., 112 parts by weight of sodium sulfate, 5 parts by weight of sodium sulfite, and 1 part by weight of a fluorescent dye were added and stirred for 10 minutes. Add 124 parts by weight of sodium carbonate, add 230 parts by weight of 40% by weight sodium polyacrylate aqueous solution and stir for 10 minutes. Add 46 parts by weight of sodium chloride and 196 parts by weight of zeolite and stir for 15 minutes to homogenize. Slurry was obtained (slurry water content 53 wt%). The final temperature of this slurry was 50 ° C.

  The slurry was supplied to a spray drying tower (counterflow type) with a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. The hot gas supplied to the spray drying tower was supplied at a temperature of 250 ° C. from the bottom of the tower, and was discharged at 110 ° C. from the top of the tower. The output of the blower inverter at that time was 80%. The obtained surfactant-carrying granule group 1 had a water content of 2.6%, a bulk density of 532 g / L, and an average particle size of 295 μm. Using this surfactant-supporting granule group, a detergent particle group was produced by the following method.

  The surfactant composition (polyoxyethylene alkyl ether / polyethylene glycol / sodium alkylbenzenesulfonate / water = 42/8/42/8: weight ratio) was adjusted to 80.degree. Next, 100 parts by weight of the surfactant-supporting granule group obtained in a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket) is charged and the main shaft (stirring blade, rotation speed: 60 r / min, Stirring at a peripheral speed of 1.6 m / s was started. In addition, 80 degreeC warm water was poured by the jacket at 10 L / min. Thereto, 50 parts by weight of the surfactant composition and 20 parts by weight of the crystalline alkali metal silicate (after treatment) 1 prepared in Example 1 were added in 2 minutes, and then stirred for 5 minutes. Furthermore, 15 parts by weight of zeolite was introduced as a surface modifier for imparting good fluidity as a detergent particle group, and a main shaft (rotation speed: 120 r / min, peripheral speed: 3.1 m / s) and a chopper ( Stirring at a rotational speed of 3600 r / min and a peripheral speed of 28 m / s was performed for 1 minute, and the detergent composition 1 was discharged. The obtained detergent composition 1 had an average particle size of 325 μm, a bulk density of 831 g / L, and a fluidity of 6.1 s. The detergent composition 1 had a caking resistance (passage rate) of 85.3%.

Example 7
A detergent composition 2 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 2 prepared in Example 2. The resulting detergent composition 2 had an average particle size of 318 μm, a bulk density of 829 g / L, and a fluidity of 6.0 s. The detergent composition 2 had a caking resistance (passage rate) of 80.5%.

Example 8
A detergent composition 3 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 3 prepared in Example 3. The obtained detergent composition 3 had an average particle size of 316 μm, a bulk density of 833 g / L, and a fluidity of 6.0 s. The detergent composition 3 had a caking resistance (passage rate) of 75.3%.

Example 9
A detergent composition 4 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 4 prepared in Example 4. The resulting detergent composition 4 had an average particle size of 320 μm, a bulk density of 828 g / L, and a fluidity of 6.1 s. The detergent composition 4 had a caking resistance (passage rate) of 81.6%.

Example 10
A detergent composition 5 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 5 prepared in Example 5. The detergent composition 5 obtained had an average particle size of 323 μm, a bulk density of 830 g / L, and a fluidity of 6.0 s. The detergent composition 5 had a caking resistance (passage rate) of 76.5%.

Comparative Example 4
A detergent composition 6 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 6 prepared in Comparative Example 1. The detergent composition 6 obtained had an average particle size of 319 μm, a bulk density of 829 g / L, and a fluidity of 6.0 s. The detergent composition 6 had a caking resistance (passage rate) of 56.5%.

Comparative Example 5
A detergent composition 7 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 7 prepared in Comparative Example 2. The resulting detergent composition 7 had an average particle size of 314 μm, a bulk density of 826 g / L, and a fluidity of 6.1 s. The detergent composition 7 had a caking resistance (passage rate) of 59.8%.

Comparative Example 6
A detergent composition 8 was produced in the same manner as in Example 6 except that the crystalline alkali metal silicate (after treatment) was changed to the crystalline alkali metal silicate (after treatment) 8 prepared in Comparative Example 3. The obtained detergent composition 8 had an average particle size of 340 μm, a bulk density of 851 g / L, and a fluidity of 7.1 s. The detergent composition 8 had a caking resistance (passage rate) of 74.2%.

The compositions and physical property evaluation results of the obtained detergent compositions are summarized in Tables 3 and 4. The compositions of the surfactant-supporting granules and the surfactant composition are summarized in Tables 5 and 6, respectively. The detergent compositions 1 to 5 obtained in Examples 6 to 10 use the crystalline alkali metal silicate (after treatment) 1 to 5 of the present invention having high storage stability, and are Comparative Examples 4 to 5. Unlike the obtained detergent compositions 6-7, it is a detergent composition excellent in all of fluidity | liquidity, caking resistance, and washing | cleaning performance. The detergent composition 8 obtained in Comparative Example 6 has the same caking resistance as that of the Examples, but is not preferable from the viewpoint of cleaning performance and fluidity.

  The cleaning composition of the present invention is suitably used as a detergent for clothing.

Claims (8)

(A) a crystalline alkali metal silicate;
(B) water, wherein (B) component is water selected from the group consisting of (i) tap water, distilled water, ion exchange water, water vapor, deionized water, and industrial water, or (ii) alkali metal Water contained in an aqueous solution or aqueous dispersion of a salt selected from the group consisting of sulfate, alkali metal carbonate, and lithium silicate,
(B) / (A) = 0.05-0.250 It mixes by weight ratio, The processing method of the crystalline alkali metal silicate whose particle growth degree by mixing is 1.5 or less. The component (A) is represented by the formula (I):
xM ₂ O.ySiO ₂ .zMeO.wH ₂ O (I)
(In the formula, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg in MeO) / Ca = 0 to 10 and w is 0 to 20.)
The processing method according to claim 1, which is a crystalline alkali metal silicate having a composition represented by:   The processing method according to claim 1 or 2, wherein the average particle diameter of the crystalline alkali metal silicate after the treatment is 300 µm or less.   The processing method in any one of Claims 1-3 which mix in the temperature range of 1-28 degreeC. Crystalline alkali metal silicate (A) is _{Na 2 O · 2SiO 2 · wH} 2 processing method O composition represented by crystalline layered claim 2-4, wherein any one silicate is sodium. The crystalline alkali metal silicate obtained by the processing method in any one of Claims 1-5 . Claim 1-5 The detergent composition contains at least one crystalline alkali metal silicates obtained by processing method according to any one. A detergent composition obtained by mixing a liquid surfactant and a crystalline alkali metal silicate obtained by the treatment method according to any one of claims 1 to 5 in a surfactant-supporting granule group.