JP4484580B2 - Surface modification treatment method - Google Patents

Description

  The present invention relates to a method for surface modification of detergent particles using detergent particles and fine powder for surface modification (surface modification powder). The present invention also relates to a method for producing detergent particles and a method for producing a detergent composition.

  Detergents cause caking to form a solidified state in which detergent particles are bonded to each other during long-term storage. Such a caking phenomenon is mainly caused by the detergent particles absorbing components such as moisture and carbon dioxide during storage. For example, due to moisture absorption, water partially dissolves the components on the surface of the detergent particles, forming a sticky portion on the surface of the detergent particles and causing caking. On the other hand, the absorption of carbon dioxide gas reacts with sodium carbonate, which is an alkaline component in the detergent, and moisture in the detergent, thereby producing needle-like crystals of sodium hydrogencarbonate and sodium sesquicarbonate on the surface of the particles. The acicular crystals are entangled with the acicular crystals on the surface of adjacent chestnut-shaped detergent particles to cause caking. The caking not only deteriorates the appearance remarkably but also makes it difficult to accurately measure the appearance.

  By the way, powder detergents for clothing are often distributed as gifts and prizes, and as a result, there are not a few amounts that stay in the home. In addition, clothing detergents are regularly sold in the market, so it is normal to buy them in bulk. In particular, in recent years, it has been sold in units of bundles (usually 8-9 pieces), and it seems that the amount of one purchase is increasing. However, there has not been a major change in the standard usage of detergents, and the average annual household usage of detergents has remained almost constant. From the above social environment, the conclusion is reached that the residence time of the detergent in the home is likely to be extended.

On the other hand, many detergent containers are made of paper. In order to improve the moisture absorption resistance and gas barrier properties, the paperboard constituting the container is devised such as a multilayer structure containing a resin film, but it cannot be said to be sufficient for long-term storage. Furthermore, the increase in environmental awareness worldwide is expected to accelerate the use of paper containers.
Against this background, there is an increasing demand for powder detergents for clothing that have excellent resistance to caking.

  In order to solve such a problem, Patent Document 1 discloses a technique for obtaining free-flowing properties by mixing a granular detergent composition and a liquid binder substance and then coating with zeolite X. Zeolite X, which is a coating powder, peels off due to stress during transportation, and a sufficient effect cannot be obtained. If the amount of the binder is large, the solubility is lowered.

In addition, Non-Patent Document 1 describes a technique for coating with a water-insoluble inorganic powder such as calcium stearate, magnesium carbonate, aluminosilicate, etc., but due to the stress that the detergent particles receive during transportation in the transportation process or manufacturing process. It is expected that sufficient effects cannot be obtained during actual use due to peeling of the coated powder.
Japanese Patent No. 2965905 Gazette of the Japanese Patent Office A collection of well-known techniques (powder detergent for clothing)

  As described above, it is clear that increasing the coverage of the detergent particles with the surface modifying powder and other coating agents is effective in improving the caking resistance. However, the conventional technology is to apply the surface modification powder by coating the surface of the detergent particles with the binder component itself or the adhesiveness of the binder component, and both of them have a considerable deterioration in solubility. It was accompanied. Accordingly, an object of the present invention is to provide a surface modification treatment method that improves the adhesion of the surface modification powder to the detergent particle surface without relying on the binder component, and the surface coverage in the treatment method is improved. An object of the present invention is to provide a method for producing a detergent particle group that is highly soluble and excellent in caking resistance, and a method for producing a detergent composition using the detergent particle group obtained by using the above-mentioned treatment method.

  In order to solve such a problem, the present inventors have intensively studied, and as a result, paying attention to the charge amount of the detergent particles and the surface modification powder, and adjusting each of them to a desired amount, The adhesion to the detergent particles was improved, and as a result, the caking resistance was improved without causing inconveniences such as a decrease in solubility, and the present invention was completed.

That is, the gist of the present invention is as follows.
[1] In the step of coating the surface of the detergent particles with the surface modifying powder, the surface modification of the detergent particles is characterized in that the absolute value of the charge amount of the surface modifying powder and / or the detergent particles is 50 V or less. Quality treatment method,
[2] A method for producing a detergent particle group using the treatment method according to [1], and [3] a method for producing a detergent composition using the detergent particle group obtained by using the treatment method according to [1].

  By using the surface modification treatment method of the present invention, the surface coverage of the fine powder for surface modification is improved without substantially adding a binder component, and a detergent particle group having good caking resistance is produced. The effect that it becomes possible to do is produced.

1. Detergent Particles The detergent particles used in the present invention are not particularly limited as long as they are particles incorporated in the detergent composition, but from the viewpoint of appearance when used as a powder detergent composition, the average particle diameter is 100 to 900 μm. The detergent particles are preferred. Such detergent particles can be manufactured through a wide variety of processes. For example, the slurry may be spray-dried to obtain detergent particles, or detergent particles obtained by stirring granulation and / or crushing granulation after spray drying are also preferable. Further, detergent particles obtained by a dry neutralization method or a dry granulation method are also preferable. Detergent particles described in Japanese Patent No. 312757 are exemplified as particularly preferred detergent particles in terms of cleaning performance and solubility.

  In addition to the detergent particles, particles that improve cleaning performance or give new functions by being contained in the detergent composition, such as bleaching agents, bleach activators, softening agents, silicone particles , Perfume particles, enzymes, granular sodium carbonate and the like. The average particle size of these particles is preferably 100 to 900 μm.

  The average particle size of the detergent particles is obtained by oscillating for 5 minutes using a standard sieve (mesh opening 2000 to 125 μm) of JIS Z 8801 and then calculating the median diameter from the weight fraction according to the size of the sieve mesh.

2. Surface Modification Powder The surface modification powder used in the present invention is a fine powder used for surface modification of the detergent particles. The average particle size of the primary particles of the surface modifying powder is preferably 10 μm or less, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 5 μm. When the average particle size is within this range, the coverage of the detergent particle group on the particle surface (surface coverage) is improved, which is preferable from the viewpoint of improving the fluidity and caking resistance of the detergent particle group. The average particle size 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.

  As the surface modifying powder, an aluminosilicate is more preferable, and a crystalline aluminometal silicate is more preferable from the viewpoint of calcium capturing ability. Other than the aluminosilicate, fine powders such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, and amorphous silica derivatives are also preferable. 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 surface modifying powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 2 to 20 parts by weight, based on 100 parts by weight of the detergent particles, and 3 to 15 Part by weight is most preferred. When the amount of the surface modifying powder used is within this range, the fluidity is improved and the consumer has a good feeling of use.
In the present invention, the average particle diameter of the surface modifying powder is the average value of the directional tangent diameter (Ferret diameter) measured by a scanning electron microscope (SEM).

3. Charge amount The present invention is a surface modification treatment method characterized in that the absolute value of the charge amount of the surface modification powder and / or the detergent particles is adjusted to 50 V or less. Therefore, it is very important to measure the charge amount of the surface modifying powder and the detergent particles. From the dielectric constant of the surface modifying powder (hereinafter also simply referred to as powder) and the detergent particles (hereinafter also simply referred to as particles) and the dielectric constant of substances used in pipes and mixing devices, either positive or negative Although it is possible to make a qualitative judgment as to whether the battery is charged, it is extremely difficult to predict the charge amount quantitatively. It is also very difficult to actually measure the charge amount of the powder and / or particles. Theoretically, electric charge creates an electric field in the vicinity of it, so if it is static, the electric field can be integrated to define the potential difference (voltage). As a technique for measuring the potential difference, an easy and reliable method has been developed. If the geometric shape of the charged body is known, the capacitance can be calculated, and the charge amount can be calculated from the capacitance and the potential difference. It can be measured. However, when the powder and particles are charged bodies, it is difficult to specify the shape, so it is practically impossible to measure the capacitance and the charge amount.

  Therefore, in the present invention, the charge amount is represented by a potential difference measured at a certain distance from the powder or particles. Specifically, by measuring the potential difference at a certain distance, the shape of each powder and particle is ignored, and it is assumed that the powder and the entire particle form one powder layer. Instead of measuring the amount of charge by measuring the potential difference across the body layer. In the present invention, the potential difference is measured 1 centimeter away from the powder or particles. In the present invention, the absolute value of the charge amount means the magnitude of a numerical value not related to the sign of the charge amount measured by the above method. Specifically, the absolute value of 50 V or less is from −50 V to +50 V. Refers to the amount of charge.

  As a device that can be used for measuring the surface potential, “High-precision electrostatic sensor SK-030 / 200” manufactured by Keyence Corporation, “Low-potential surface potential meter KSD-0303” manufactured by Kasuga Electric Co., Ltd., manufactured by Trek Various non-contact type surface potential meters such as “Surface potential meter Model 344” can be used.

The absolute value of the charge amount of the powder or particles is 50 V or less. In particular, when the absolute value of the charge amount of the surface modification powder is large, electrostatic repulsion between the surface modification powders becomes intense, which is not preferable for increasing the thickness of the coating layer. In particular, in order to improve the caking resistance of the detergent particles, it is important to increase the thickness of the coating layer. As a result, the smaller the absolute value of the surface modification powder, the better.
In the present invention, the absolute value of the charge amount of the powder or particles may be adjusted to the above range when the powder and particles are mixed.

4). Method for adjusting charge amount The method for adjusting the charge amount of the surface modification powder and the detergent particles includes the following.

4-A. Adjustment of the charge amount by the surfactant By mixing the surfactant with the surface modification powder, the charge amount of the surface modification powder can be adjusted. For example, by adding a surfactant having an antistatic function to the surface modification powder, the absolute value of the charge amount of the surface modification powder can be reduced. Further, by adding a surfactant having a function as a charge control agent to the detergent particles, the absolute value of the charge amount of the detergent particles can be reduced.

  As the surfactant that can be used for adjusting the charge amount, various combinations are conceivable depending on the surface properties of the surface modifying powder and the detergent particles. For example, a cationic surfactant and / or an amphoteric surfactant is preferred from the viewpoint of reducing the absolute value of the charge amount of negatively charged particles and powder. As the cationic surfactant, a quaternary ammonium salt is preferable, and an alkyltrimethylammonium chloride having 12 to 16 carbon atoms and a dialkyldimethylammonium chloride having 12 to 18 carbon atoms are particularly preferable. The amphoteric surfactant is preferably an alkylbetaine having 12 to 18 carbon atoms, and particularly preferably alkyldimethylcarboxybetaine.

  The amount of the surfactant is preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight based on the surface modifying powder or the detergent particles. This amount is preferably 10% by weight or less from the viewpoint of maintaining the fluidity of the detergent particles, and preferably 0.1% by weight or more from the viewpoint of obtaining an effect sufficient to control the charge amount. The amount of the surfactant is preferably from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight, based on the surface modifying powder. The amount of the surfactant is preferably 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 2% by weight with respect to the detergent particles.

  Further, as a method for adding the surfactant, any method may be used as long as it ensures sufficient mixing with the surface modifying powder and the detergent particles. However, when mixing the liquid surfactant, it is preferable to use a technique of jetting and spraying the surfactant.

  The pulverizing apparatus and mixing apparatus used for intimately mixing the surfactant and the surface modifying powder or detergent particles 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 crushing by pressure or impact force, such as a jaw crusher, a gyratory crusher, a roll crusher, or a roll mill.
(2) A striking plate is fixed around a rotor that rotates at high speed, and a processing object is pulverized by a shearing force generated by the rotor and the striking plate, such as a hammer mill, an impact crusher, and a pin mill.
(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, and includes, for example, 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. For example, a ball mill, vibration mill, planetary mill, etc. 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, examples of the mixing apparatus include the following.
(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 Paulek 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 this 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 1 second to 50 minutes, more preferably 10 seconds to 10 minutes. It is also possible to contact / mix the surfactant with the surface modifying powder and the detergent particles in a gaseous, vapor or aerosol-like state without using a mixer.

4-B. Adjustment of charge amount by air ions The charge amount of the surface modifying powder and the detergent particles can be adjusted by spraying ionized air. For example, by blowing air ions having a charge opposite to the charge amount of the surface modification powder and the detergent particles onto the surface modification powder and the detergent particles, the absolute value of the charge amount can be reduced by canceling the charge. it can.

  A commercially available static eliminator can be used for the operation using such air ions. As a commercially available static eliminating device, there are a type that blows air ions onto an object by blowing air, and a type that ionizes ions in the atmosphere by irradiating soft X-rays. When the object is powder or particles, the soft X-ray irradiation type is preferable as static elimination efficiency because it is not necessary to carry air ions by blowing air, but a protective device for shielding X-rays is required. Therefore, the type in which air ions are blown by air is preferable in terms of safety. In the case of a type in which air ions are blown, it is preferable to use a charge amount measuring device together because the amount of air ions generated can be changed in accordance with the charge amount of the object to be neutralized, and the neutralization efficiency is increased.

  As a type of soft X-ray irradiation, for example, a photo ionizer (light irradiation type static eliminator) manufactured by Hamamatsu Photonics Co., Ltd. can be cited. For example, a blower type direct current static eliminator, etc. Regarding the processing method using the static eliminator, the position of the device, the surface modifying powder, and the detergent particles is reduced because the scattering of air ions and the attenuation of soft X-rays are suppressed if the distance between the device and the processed material is short. The performance is preferably improved, and conversely, when the distance is increased, the region where the charge can be removed becomes wider. The distance between these devices and the object is preferably 0.1 to 1.0 m, and more preferably 0.1 to 0.6 m. Regarding the processing time in the apparatus, the shorter the time, the better the production efficiency, but the longer the processing time, the better the static elimination effect. The treatment time is preferably 0.1 to 60 seconds. Note that the timing of bringing the ionized air into contact with the detergent particles or the surface modifying powder is preferably just before mixing these particles and the powder from the viewpoint of suppressing the change in the charge amount after static elimination.

4-C. Adjustment of charge amount by friction The detergent particles and the surface modifying powder are charged by friction with the apparatus and piping during the manufacturing process, and the charge amount changes. For example, when particles are pneumatically transported, a phenomenon is known in which the charge amount of the particles increases due to friction caused by collision between the inner wall of the transport pipe and the particles and between the particles. Generally, the materials used for piping and equipment are mostly iron and stainless steel, so the surface modification powder and detergent particles often have a negative charge due to friction. Therefore, in order to coat the surface modifying powder more with detergent particles, it is effective to suppress charging by reducing the frictional resistance with the apparatus and piping during the manufacturing process.

  In order to suppress the friction, it is effective to apply a lubricant to the inner wall of the apparatus or piping. Examples of the lubricant include monohydric alcohol esters of fatty acids having 12 to 18 carbon atoms (for example, methyl esters), monobasic alcohol esters of polybasic acids (for example, adipic acid / phthalic acid), fatty acid esters of polyhydric alcohols, and the like Derivatives and the like are preferred, among which 2-ethylhexyl palmitate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, stearyl stearate, diisodecyl adipate, polyoxyethylene bisphenol A laurate, pentaerythritol monooleate Particularly preferred are pentaerythritol monostearate and the like.

The methods 4-A to 4-C may be used in combination.
It is said that the treatment by the 4-A to 4-C charge amount adjustment method suppresses electrical repulsion between the detergent particles and the surface modifying powder and improves the coverage of the detergent particles by the surface modifying powder. The effect is expressed. At the same time, the electrical repulsion between the surface modifying powders can be suppressed, and the coating layer formed on the surface of the detergent particles by the surface modifying powder can be made thicker. Therefore, for this purpose, it is preferable that the surface modifying powder is close to an uncharged state in the step of coating the detergent particles with the surface modifying powder. If the surface modifying powder becomes nearly uncharged, the electrical repulsion with the detergent particles becomes weak, and the electrical repulsion between the surface modifying powders is also suppressed.

  The absolute value of the charge amount is preferably 150 V or less, more preferably 100 V or less, and particularly preferably 50 V or less. In addition, when the charge amount of the detergent particles is the same as that of the powder for surface modification, it is preferable that the absolute value is small, the absolute value is more preferably 150 V or less, further preferably 100 V or less, and particularly preferably 50 V or less. .

  The coverage of the detergent particles with the surface modifying powder can be measured using a surface analysis device such as FT-IR / PAS as exemplified in the examples. The coverage is preferably 1.4 or more, more preferably 1.5 or more from the viewpoint that the higher the coverage, the smaller the exposed area of the detergent particles. The thickness of the coating layer can be measured by cleaving the particles after the coating operation and observing with a scanning electron microscope. The thickness of the coating layer is preferably 7 μm or more, more preferably 8 μm or more, and particularly preferably 9 μm or more from the viewpoint that the thicker the coating layer, the more the contact between the detergent particles is prevented.

  In addition, in the treatment method of the present invention, from the viewpoint of increasing the solubility of the detergent particles, in the step of coating the surface of the detergent particles with the surface modifying powder, a substantially liquid binder component may not be added. preferable. Although it does not specifically limit as a liquid binder component, Surfactant which can be used for the detergent particle group mentioned later, a water-soluble polymer, etc. are mentioned.

5). Solubility and caking resistance of detergent particle group As described above, the detergent particle group obtained by using the treatment method of the present invention has a fine powder (surface for surface modification) even if it contains substantially no binder component. The surface coverage by the modifying powder) is high. Therefore, by using the treatment method of the present invention, a detergent particle group having excellent caking resistance can be obtained without impairing solubility.

  As one of the methods for evaluating the solubility, after stirring in cold water at 5 ° C. for 1 minute, the ratio of passing through the mesh is obtained as a weight percentage, and the numerical value can be used as an index. Although the dissolution rate is not particularly limited, the detergent particle group coated with the surface modification powder whose charge amount has been manipulated is the detergent particle group coated with the surface modification powder which has not been treated. In comparison, the dissolution rate is preferably within ± 5 points, and more preferably within ± 4 points.

  As one of the methods for evaluating the caking resistance, after the detergent particles are stored in a high humidity atmosphere, the ratio of passing through a sieve having a sieve opening of 5 mm is obtained as a weight percentage, and the evaluation method using the numerical value as an index. There is. The passing rate of the sieve is not particularly limited, but the detergent particles coated with the surface modifying powder whose charge amount has been manipulated are compared with the detergent particles coated with the unmodified surface modifying powder. Thus, the sieve passing rate is preferably increased by 5 points or more, more preferably increased by 10 points or more.

  In addition, a dissolution rate and a sieve passage rate can be measured according to the method as described in the below-mentioned Example.

6). Detergent Particle Group The detergent particle group of the present invention can contain a crystalline alkali metal silicate, a surfactant, a water-soluble polymer, a water-soluble salt, a water-insoluble substance and the like.

Examples of the crystalline alkali metal silicate that can be used in the detergent particles of the present invention include, for example, 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)
A composition represented by the formula is preferred. 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 composition formula (I), y / x = 1.0 to 2.1, z / x = 0.001 to 1 0.0 alkali metal silicate. 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 crystalline alkali metal silicates, from the viewpoint of scavenging ability of hardness components such as calcium and magnesium, the most preferable are x = 1, y = 2, z = 0 in the formula, and M = Na. Crystalline layered sodium disilicate Na ₂ Si ₂ O ₅ .wH ₂ O. 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. Preferred crystalline layered sodium disilicates are 0 to 40% by weight α-sodium disilicate, 0 to 40% by weight β-sodium disilicate, 40 to 100% by weight δ-sodium disilicate, It consists of an amorphous fraction in a proportion of ˜40% by weight. Particularly preferred crystalline layered sodium disilicate is 7 to 21% by weight α-sodium disilicate, 0 to 12% by weight β-sodium disilicate, 65 to 95% by weight δ-sodium disilicate. , And consists of an amorphous fraction in a proportion of 0 to 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, those exemplified above may be used alone, or several kinds may be mixed and used as a mixture.

  The amount of the crystalline alkali metal silicate is preferably 1 to 14% by weight, more preferably 3 to 12% by weight, from the viewpoint of alkali buffering ability and calcium capturing ability in the detergent particle group.

The surfactant that can be used in the detergent particle group 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 counter ions 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 carbon number is 10-18, more preferably 12-14, and the average added mole number is preferably 5-30, more preferably 7-30, still more preferably 9-30, particularly preferably 11-30. An ethylene oxide (hereinafter referred to as EO) adduct of an alcohol, 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
[Wherein, R represents a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group or an alkenyl group, EO represents an ethylene oxide group, PO represents a propylene oxide group, and X, Y, and Z represent the average number of added moles, respectively. ]
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 amount of the surfactant is preferably 5 to 35% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 35% by weight, more preferably 20 to 30% by weight from the viewpoint of cleaning performance in the detergent particle group. % Is particularly preferred.

  Examples of the water-soluble polymer contained in the detergent particles 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.

  In addition, polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), polypropylene glycol (PPG) and the like can be mentioned. PVP is preferable as an anti-color transfer agent, and PEG and PPG having a molecular weight of about 1,000 to 20,000 are preferable because they improve paste viscosity characteristics generated when the powder detergent contains water.

  The content of the water-soluble polymer in the detergent particle group is preferably 2 to 25% by weight, more preferably 2.5 to 20% by weight, still more preferably 3 to 15% by weight, and particularly preferably 3.5 to 10% by weight. preferable. Within this range, the strength of the detergent particles is sufficiently high.

  In the detergent particle group of the present invention, the water-soluble salts used as an alkaline buffer and a filler are preferably those described below. Examples of water-soluble salts include water-soluble inorganic salts (for example, alkali metal salts, ammonium salts, or amine salts) such as carbonic acid, sulfuric acid, hydrogen carbonate, sulfurous acid, hydrogen sulfate, and phosphoric acid. 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 particle group is preferably 10 to 45% by weight, more preferably 15 to 40% by weight, still more preferably 20 to 37.5% by weight, and particularly preferably 25 to 35% by weight. If it is in these ranges, the particle strength of the detergent particles is sufficiently high, and the solubility of the detergent particles is also preferable.

  In the detergent particle group 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 WO 98/42622 is also suitable as a 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 particle group is preferably 5 to 55% by weight, more preferably 10 to 50% by weight, still more preferably 15 to 45% by weight, and most preferably 20 to 40% by weight. Within this range, a detergent particle group 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.

  Further, the detergent particle group can contain auxiliary components such as known fluorescent dyes, pigments, dyes, enzymes and the like. The content of the auxiliary component is preferably 0.1 to 15% by weight in the detergent particle group, more preferably 0.1 to 10% by weight, and particularly preferably 0.1 to 5% by weight.

7). Manufacturing method of detergent particle group The manufacturing method of the detergent particle group of the present invention is characterized by using the surface modification treatment method of the present invention, and the storage stability of the resulting detergent particle group by having such a characteristic. In particular, there is an advantage that the caking resistance is excellent. The production method is not particularly limited, and an operation for adjusting the charge amount of the detergent particles and the surface modifying powder may be included before the coating operation. Although the manufacturing method of a detergent particle group is shown below as an example, it is not necessarily limited to this manufacturing method.

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): A step of mixing the surfactant-supporting granules obtained in step (b), the surfactant composition, and the crystalline alkali metal silicate under the condition that the surfactant composition is in a liquid state. ,
Step (d): a step of adjusting the absolute value of the charge amount of the mixture (detergent particles) and / or fine powder (surface modifying powder) obtained in Step (c) to 50 V or less,
Step (e): The step comprises mixing the detergent particles whose charge amount has been adjusted in step (d) and the surface modifying powder, and coating the surface of the detergent particles with the surface modifying powder to obtain a detergent particle group. . 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. By making the temperature of the slurry within a certain range, the solubility of the water-soluble salts is increased, and the increase in the viscosity of the slurry is suppressed, which is preferable in terms of pumping property. 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 step, 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. In addition, when the batch method is used, the mixing method for the mixer is as follows: (1) First, the surfactant-supporting granule group is charged into the mixer, and then the surfactant is added; (2) The interface is added to the mixer. (3) After a part of the surfactant-carrying granule group is charged into the mixer, the remaining surfactant-carrying granule group and surfactant are charged. And so on in small amounts; 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. In the case of sodium acid, a surfactant mixture liquid that can be easily sprayed can be obtained by adjusting the ratio of the two in the range of 1: 1.4 to 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, a strong shearing force is not easily applied to the surfactant-carrying granules (the surfactant-carrying granules are not easily disintegrated). 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), it is possible to add a crystalline alkali metal silicate 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. . The crystalline alkali metal silicate is preferably added in this step (c), but a part thereof may be added in the step (e) as a surface modifier, or as crystalline alkali metal silicate granules, After blending may be used.

  When adding crystalline alkali metal silicate, add powder builder and / or powder surfactant other than crystalline alkali metal silicate before, simultaneously with, during and after addition. Is also possible. 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 buffering ability such as potassium carbonate, and a base that enhances ionic strength such as sodium sulfate.

  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)>
Using the charge amount adjusting method described above, the absolute value of the charge amount of the mixture (detergent particles) and / or the surface modifying powder obtained in the step (c) is adjusted to 50 V or less.

  The surface modifying powder is particularly preferably an aluminosilicate, which may be crystalline or amorphous, but is preferably crystalline from the viewpoint of calcium scavenging ability. 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 having an average particle size of 10 μm or less can be used as a powder for surface modification. Further, a metal soap having a primary particle size of 0.1 to 10 μm, preferably 0.5 to 5 μm, a powdered surfactant (for example, alkyl sulfate) and a water-soluble organic acid salt can be used in the same manner.

  The amount of the surface modifying 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 surface modifying powder used is within this range, the fluidity is improved and the consumer has a good feeling of use.

  Regarding the method for adjusting the charge amount, it is important to distribute the lubricant to the process in advance in order to reduce the friction in the process.

  Further, when a surfactant is added, it may be added in advance, but it is preferably performed immediately before the coating operation. As a method for adding the surfactant, it may be added continuously or batchwise treatment may be performed.

  When using a commercially available static eliminator, it is preferable to perform an operation for adjusting the charge amount immediately before the coating operation. The operation may be performed continuously or by batch processing.

  In the charge amount adjustment treatment, it is preferable to treat the detergent particles and the surface modifying powder separately. The processing method may be continuous or batch processing.

<Process (e)>
In the present invention, in order to modify the particle surface of the detergent particle group carrying the surfactant in step (c), the surface modifying powder whose charge amount has been adjusted in step (d) is added. The step (step (e)) is performed in one step or two steps.

  The apparatus used in the step (e) is not particularly limited, and a known mixer can be used, but the mixer exemplified in the above step (c) is preferable. From the viewpoint of the dispersion efficiency of the surface modifying powder, an apparatus with good mixing efficiency is preferable, and in order to prevent the surface modifying powder attached to the detergent particles from peeling off, an apparatus that is not easily subjected to a strong shearing force is preferable. . Particularly preferred among the mixers listed in step (c) is a mixer of a type in which a horizontal mixing tank has a stirring shaft at the center of a cylinder and a stirring blade is attached to this shaft to mix the powder (horizontal mixing). Machine), there is a Redige mixer, a Proshare mixer, etc.

  Further, it is preferable that the surface coverage is increased when the detergent particles are once coated with the above-mentioned mixer and then subjected to the second-stage coating with another mixer that is less susceptible to shearing force. As the mixer used for the coating process in the second stage, a rotary cylindrical mixer such as a rotary mixer or a drum mixer is preferable.

8). Detergent composition Moreover, a detergent composition can be prepared by using the detergent particle group obtained through the step (e) and mixing with other detergent components if necessary. Therefore, this invention relates to the manufacturing method of the detergent composition using the detergent particle group obtained by using the said surface modification processing method. As other detergent components, for example, a granulated product of crystalline alkali metal silicate, 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. Further, the upper limit of the content of the detergent particle group is preferably 99.9% by weight or less, and more preferably 99% by weight or less.

  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.

  Although it does not specifically limit as a use of the said detergent composition, It is used as washing | cleaning detergents for clothes, dishwashing detergents, residential detergents, automobile detergents, toothbrushes, body detergents, metal detergents and the like.

Although this invention is illustrated below, this invention is not limited to this. In the examples and comparative examples, the physical properties of the surface modifying powder, the detergent particles, and the detergent particles were evaluated by the following test methods.
(Moisture): Measured by a method defined by JIS K 0068.
(Bulk density): Measured by a method defined by JIS K 3362.
(Average particle diameter): After vibrating for 5 minutes using a standard sieve of JIS Z 8801 (mesh size: 2000 to 125 μm), the median diameter was calculated from the weight fraction depending on the size of the sieve mesh.

(Surface coverage): It is possible to quantify the coverage by the modifier on the surface of the detergent particles in a non-destructive manner using Fourier transform infrared photoacoustic spectroscopy (FT-IR / PAS). That is, the spectrum of the surface modifying powder and the detergent particles was measured, and a peak that did not overlap with each other was selected as the index peak. The FT-IR / PAS of the detergent particle group was measured, and the ratio of (index peak intensity of surface modifying powder) and (index peak intensity of detergent particles) was defined as the surface coverage. In the examples of the present invention, the peak near 1650 cm ⁻¹ derived from zeolite crystallization water is used as the index peak of the surface modifying powder, and —COO— of sodium polyacrylate is used as the index peak of the detergent particles. A peak around 1580 cm ⁻¹ derived from the group was used. A larger value of FT-IR / PAS indicates that the surface of the detergent particles is coated with the surface modifying powder.

(Coating layer thickness): With respect to the detergent particle group classified when the average particle diameter was determined, the particles on each sieve were cleaved according to the weight percentage value. For example, when the weight percentage of 250 on and 355 passes was 25%, 25 detergent particles were cleaved, and the thickness of the surface modification powder of the cleaved particles was observed with an operation electron microscope. The average value of a total of 100 detergent particles was used as the thickness of the coating layer of the detergent particles.

(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.) A container with an open top of 13.5 cm was made. In this box, 1200 g of detergent particle group sample was placed. This was left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 70%, and the caking state was determined after 8 days. The determination was performed 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 passing rate of the sample after the test. The higher the sieve passing rate, the higher the caking resistance, which is a preferable physical property as a detergent particle group.

(Solubility): Measurement conditions: 1.000 g ± 0.010 g of sample was put into 1.00 L ± 0.03 L of water having a hardness of 4 ° DH at 5 ° C. ± 0.5 ° C., and placed in a 1 L beaker (inner diameter 105 mm). After stirring for 120 seconds with a cylindrical stirrer (length: 35 mm, diameter: 8 mm) at a rotation speed of 800 rpm, the dissolved residue was filtered with a standard sieve (mesh size: 300 μm) defined in JISZ8801. The dissolution rate V of the classified particle group was calculated by the following formula (a).
V = (1-T / S) × 100 (%) (a)
(Here, S represents the input weight (g) of each classified particle group, and T represents the dry weight (g) of the dissolved residue of each classified particle group remaining on the sieve after filtration).

(Charge amount): Measured by bringing the sensor part of a high-precision electrostatic sensor SK-030 / 200 manufactured by Keyence Corporation close to 1 cm above the powder layer or particle group. The average value at 5 locations was taken as the charge amount.

In this example, the following raw materials were used unless otherwise specified.
Sodium sulfate: anhydrous neutral sodium sulfate (manufactured by Shikoku Kasei Co., Ltd.)
Sodium sulfite: Sodium sulfite (Mitsui Chemicals)
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: grilled salt S (manufactured by Nippon Salt Corporation)
Crystalline sodium aluminosilicate (zeolite): Zeobuilder (4A type, average particle size: 3.5 μm, manufactured by Zeobuilder)
Polyoxyethylene alkyl ether: Emulgen 108KM (Ethylene oxide average addition mole number: 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)
Crystalline layered sodium disilicate: Prefeed N (manufactured by Tokuyama Siltech Co., Ltd.)

Example 1
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 95 ° C. from the top of the tower. The output of the blower inverter at that time was 70%. 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-carrying granule group 1, detergent particle groups were produced by the following method.

  100 parts by weight of the surfactant-bearing granules 1 and 20 parts by weight of crystalline layered sodium disilicate obtained in a Redige mixer (Matsuzaka Giken Co., Ltd., volume 130 L, with jacket) were added to the main shaft (stirring) Stirring with a blade, rotation speed: 60 r / m, peripheral speed: 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 a surfactant composition (polyoxyethylene alkyl ether / polyethylene glycol / sodium alkylbenzenesulfonate / water = 42/8/42/8) heated to 80 ° C. was added in 2 minutes, and then 5 Stirring was performed for a minute. After completion of the stirring, the detergent particles were discharged from the Redige mixer, transported by a vibrating conveyor, and supplied into a φ400 mm concrete mixer. The charge amount of the detergent particles in the concrete mixer was -20V (absolute value 20V).

20 parts by weight of zeolite was placed in a 9 L Henschel mixer (Mitsui Miike Koki Co., Ltd., FM10B), the jacket temperature was set to 20 ° C., and the mixture was stirred at 3500 r / m, while 0.2 parts by weight of zwitterionic surface activity. The agent (alkyl dimethyl carboxymethyl betaine: trade name Amphitol 20BS) was added over 30 seconds. Thereafter, the mixture was stirred at 3500 r / m for 90 seconds to obtain surface modifying powder 1. The surface modification powder 1 (10 parts by weight) was used with a transport pipe having an inner diameter of 42.6 mm and a pipe length of 23.5 m, an air volume of 1.2 m ³ / min, a transport pressure of 0.8 kgf / cm ² , and an original pressure of 1 It was pneumatically transported under the condition of 0.0 kgf / cm ² and transported into the concrete mixer supplied with the detergent particles. The charge amount of the surface modifying powder 1 after pneumatic transportation was −35V. A detergent particle is coated with the surface modifying powder 1 by operating a φ400 mm concrete mixer (8 baffles) at a rotation speed of 14 r / m, a centrifugal effect of 0.04, and an inclination angle of 10 ° for 180 seconds. Group 1 was obtained. The surface coverage of the detergent particles was 1.85 (−) in terms of FT-IR / PAS. The caking resistance was 82 (%) in terms of the sieve passing rate.

Example 2
Except that the zwitterionic surfactant of Example 1 was changed to a cationic surfactant (lauryltrimethylammonium chloride: trade name Cotamine 24P), the surface modification powder 2 and detergent particles were all used in the same manner as in Example 1. Group 2 was obtained. After the air transportation, the charge amount of the surface modifying powder was −30V. The surface coverage of the detergent particle group 2 was 1.78 (−) in terms of FT-IR / PAS. The caking resistance was 80 (%) in terms of the sieve passing rate.

Example 3
10 parts by weight of zeolite was pneumatically transported and supplied to a concrete mixer. The charge amount of the zeolite after pneumatic transportation was -350V. The zeolite was neutralized with a compact static blower (SJ-F010) manufactured by Keyence for 1 minute to obtain a powder 3 for surface modification having a charge amount lowered to -35V. The surface-modifying powder 3 was used for coating treatment under the same operating conditions as in Example 1 to obtain detergent particle group 3. The surface coverage of the detergent particle group 3 was 1.74 (−) in terms of FT-IR / PAS. The caking resistance was 77 (%) in terms of the sieve passing rate.

Comparative Example When 10 parts by weight of zeolite was pneumatically transported and supplied to a concrete mixer, the charge amount was -360V. In particular, the coating treatment was performed under the same operating conditions as in Example 1 without performing the charge amount adjustment operation, and a detergent particle group 4 was obtained. The surface coverage of the detergent particle group 3 was 1.03 (−) in terms of FT-IR / PAS. The caking resistance was 58 (%) in terms of the sieve passing rate.

  Table 1 summarizes the charge amount of the surface modifying powder, the FT-IR / PAS value of the detergent particles, and the sieve passing rate. In Examples 1 to 3, the obtained surface modifying powder had an absolute value of the charge amount reduced before starting the coating process, and the electrical charge between the detergent particles and the surface modifying powder was reduced. It can be seen that by suppressing the repulsion, the surface coverage is significantly higher than in the comparative example in which the charge amount is not adjusted. In addition, it can be seen that the caking resistance is improved by increasing the surface coverage. Furthermore, in Examples 1-3, since the binder component which affects solubility is not included, it turns out that there is no difference with the sample of a comparative example also regarding a dissolution rate.

  The detergent composition obtained by the present invention is suitably used as a laundry detergent, dish detergent, residential detergent, automobile detergent, toothbrush, body detergent, metal detergent and the like.

Claims (8)

Of Table Men'aratame protein powder及beauty detergent particles, after adjusting the absolute value of it to the 50V or less by reducing the charge amount of the powder for at least the surface modification, the surface modifying powders and detergent particles mixed Then, the surface modification treatment method of the detergent particles , wherein the detergent particle surface is coated with the surface modification powder .   The processing method according to claim 1, wherein the absolute value of the charge amount of the surface modifying powder and / or the detergent particles is reduced by adding an amphoteric surfactant and / or a cationic surfactant.   The processing method according to claim 1 or 2, wherein the absolute value of the charge amount of the surface modifying powder and / or the detergent particles is reduced by blowing ionized air.   The processing method according to any one of claims 1 to 3, wherein the surface of the detergent particles is coated with a surface modifying powder without adding a substantially liquid binder component.   The processing method according to claim 1, wherein the surface modifying powder is a crystalline aluminometal silicate. The processing method according to claim 1, wherein the charge of the detergent particles and the charge of the surface modifying powder have the same sign. The manufacturing method of the detergent particle group using the processing method in any one of Claims 1-6 . The manufacturing method of the detergent composition using the detergent particle group obtained using the processing method in any one of Claims 1-6 .