JP4339043B2 - Surfactant-supporting granules - Google Patents

Description

  The present invention relates to a surfactant-supporting granule group, a production method thereof, a detergent particle group obtained using the surfactant-supporting granule group, and a detergent composition containing the detergent particle group.

  In order to use a liquid surfactant as a powder detergent, there is a method of obtaining a powder detergent by supporting the surfactant on a powder. In this case, it is desirable that the powder has a large surfactant carrying capacity (absorption amount).

In the prior art, it is disclosed that the granule group contains 0 to 10% by weight of a surfactant for improving the drying efficiency or 5 to 25% by weight for improving the caking resistance (Patent Document). 1).
However, the granule group obtained by spray-drying a slurry containing a surfactant has a film formed on the surface, so that the absorption rate for the liquid surfactant composition is reduced and the formation of depressions is inhibited. And poor oil absorption are disclosed (Patent Documents 2 and 3).
Japanese National Patent Publication No. 11-829830 International Publication No. 00/077158 Pamphlet International Publication No. 00/077148 Pamphlet

  Therefore, the present inventors have made various studies on the above points, and in the slurry before producing the surfactant-carrying granule group, a predetermined amount of a specific compound is contained, and spray drying is performed. Surprisingly, it has been found that granules having a large particle strength and pore volume can be obtained, and the amount of the surface coating agent (zeolite) can be reduced as compared with granules containing no surfactant.

  Accordingly, an object of the present invention is an oil absorbing agent and a surface coating agent that are added after mixing a surfactant composition and a surfactant-supporting granule group with sufficient bulk density for use in a compact detergent. An object of the present invention is to provide a surfactant-supporting granule group which can reduce the blending amount of zeolite or the like, or can be blended with a large amount of a surfactant composition, has excellent surfactant-supporting ability and has a large particle strength, and a method for producing the same. . Another object of the present invention is to provide a detergent particle group containing a mononuclear detergent particle group in which a surfactant composition is supported on the surfactant-supporting granule group.

That is, the gist of the present invention is as follows.
[1] A surfactant-supporting granule group obtained by spray-drying a slurry containing a water-soluble polymer, a water-soluble salt and a compound represented by the following formula [1],
R—O (CH ₂ CH ₂ O) n—SO ₃ M [1]
(In the formula, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, average added mole number n is 0 to 7, M represents Na, K, NH ₄ or triethanolammonium)
[2] A method for producing a surfactant-supporting granule group comprising a step of spray-drying a slurry containing a water-soluble polymer, a water-soluble salt and a compound represented by the formula [1],
[3] A detergent particle group in which 1 to 100 parts by weight of a surfactant composition is supported with respect to 100 parts by weight of the surfactant-carrying granules as described in [1] above, having an average particle size of 150 to 750 μm Further, the present invention relates to a detergent composition comprising a detergent particle group having a bulk density of 500 g / L or more, and [4] the detergent particle group described in [3] above.

  By using the surfactant-supporting granule group of the present invention, it becomes possible to blend a large amount of the surfactant composition or to reduce the blending amount of zeolite, which is an oil absorbent and a surface coating agent, and is excellent in cleaning performance and caking property. The effect that a detergent particle group is obtained is produced.

As described above, the granule group for supporting a surfactant of the present invention comprises a water-soluble polymer, a water-soluble salt, and a formula [1]:
R—O (CH ₂ CH ₂ O) n—SO ₃ M [1]
(In the formula, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, average added mole number n is 0 to 7, M represents Na, K, NH ₄ or triethanolammonium (TEA)).
The slurry containing the compound represented by formula (1) is obtained by spray-drying, and having such a configuration has a sufficient bulk density for use in a compact detergent, and further has a surfactant composition and an interface. Particles for reducing the amount of the oil-absorbing agent added after mixing the particles for supporting the active agent and the surface coating agent, such as zeolite, or having a large amount of a surfactant composition, have excellent surfactant-supporting ability, and particles There is an effect that a granule group for supporting a surfactant having a high strength can be obtained.

1. Composition of Granules for Carrying Surfactant The granule group for carrying a surfactant of the present invention is mainly composed of a water-soluble polymer (A), a water-soluble salt (B) and a compound represented by the formula [1]. Except for the amount of water, it is essentially the same as the granule group at the end of step (2) described below.

  Examples of the water-soluble polymer (A) include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, and sugars. Among these, from the viewpoint of detergency, acrylic acid homopolymers having a weight average molecular weight of 2000 to 100,000, acrylic acid / maleic acid copolymers, or salts thereof are preferred.

  The water-soluble salts of the component (B) are water-soluble typified by alkali metal salts, ammonium salts or amine salts having carbonate, hydrogen carbonate, sulfate, sulfite, hydrogen sulfate, hydrochloric acid or phosphate. And low molecular weight water-soluble organic salts having a molecular weight of less than 2000, such as citrate and fumarate. Of these, hydratable inorganic salts such as sodium carbonate and sodium sulfate are preferred from the viewpoint of crystallization promotion.

In the formula [1], R is preferably an alkyl group having 8 to 18 carbon atoms from the viewpoint of obtaining high particle strength and excellent ability to support a surfactant. n represents the average number of added moles, and is 0 to 7, preferably 0 to 3, more preferably 0 from the viewpoint of obtaining an excellent ability to support a surfactant. As M, Na, K, NH ₄ or TEA is preferably used. Among them, preferred examples of the compound represented by the formula [1] include compounds in which R is an alkyl group having 12 to 18 carbon atoms, n is 0 to 2 and M is Na or K, and R is 12 carbon atoms. More preferred are compounds of ˜18 alkyl groups, n = 0 and M = Na. Specific examples thereof include sodium alkyl sulfate and sodium polyoxyethylene alkyl sulfate. The compound represented by the formula [1] is preferably in the form of a powder from the viewpoint of obtaining an excellent ability to support a surfactant.

  In addition, as a substitute for the whole or a part of the compound represented by the formula [1] used in the present invention, 1 of an alkaline earth metal salt compound of a sulfate ester having an alkyl group or an alkenyl group having 8 to 18 carbon atoms Species or two or more can also be used.

  As the composition of the surfactant-carrying granule group, the component (A): (B) component is 2 to 30% by weight: 5 in order to achieve both the carrying ability and the particle strength of the obtained surfactant-carrying granule group. It is preferably -78 wt%, more preferably 3-20 wt%: 10-67 wt%, and particularly preferably 5-20 wt%: 20-55 wt%.

  The content of the compound represented by the formula [1] is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less from the viewpoint of particle strength. From the viewpoint of obtaining an excellent ability to support a surfactant, 0.001% by weight or more is preferable, more preferably 0.003% by weight or more, still more preferably 0.006% by weight or more, that is, for supporting a surfactant. 0.001 to 3 weight% is preferable in a granule group, 0.003 to 1 weight% is more preferable, and 0.006 to 0.5 weight% is still more preferable.

  In addition, the surfactant-supporting granule group preferably further contains a water-insoluble inorganic substance from the viewpoint of particle strength and cleaning performance.

  Examples of water-insoluble inorganic substances include aluminosilicates, silicon dioxide, hydrated silicate compounds, perlite, and clay compounds represented by bentonite. Of these, crystalline aluminosilicates such as zeolite are preferable because they act as sequestering agents in the detergent composition. The average particle diameter of the primary particles of the crystalline aluminosilicate used here can be measured with a scanning electron microscope (SEM) or the like. The average particle size is preferably about 0.1 to 20 μm, and an aggregate of primary particles can be used. The content of the water-insoluble inorganic substance is preferably 20 to 90% by weight, more preferably 30 to 75% by weight, and still more preferably 40 to 70% by weight in the surfactant-supporting granule group.

  The surfactant-supporting granule group may also contain auxiliary components such as fluorescent dyes, pigments and dyes suitable for the final detergent composition.

  The surfactant-supporting granule group of the present invention having such a composition can be produced, for example, as follows.

2. Method for producing surfactant-supporting granule group [about step (1) (slurry preparation step)]
Step (1) is a step of preparing a slurry for preparing a surfactant-supporting granule group. The slurry is mainly composed of the component (A), the component (B), the compound represented by the formula [1], and water, and is prepared in a state where liquid can be fed with a pump. Preferably, the slurry has a water content of 30 to 70% by weight, more preferably 35 to 60% by weight, and still more preferably 38 to 55% by weight. Moreover, the temperature of a slurry becomes like this. Preferably it is 30-80 degreeC, More preferably, it is 40-70 degreeC. Within this range, the water-soluble polymer (A) and water-soluble salts (B) (hereinafter referred to as water-soluble components (A, B)) are preferable in terms of the dissolution rate and the viscosity of the slurry, which is preferable.

  In addition, the order of adding and mixing the components is not particularly limited, but after adding the components (A) and (B), the surfactant represented by the formula [1] is added to the interface. There is an advantage that the activator carrying ability is further improved and preferable. Specific examples include a method of preparing a slurry by mixing a liquid containing the components (A) and (B) and a compound represented by the formula [1].

[Regarding Step (2) (Step of Preparing Surfactant-Supporting Granules)]
Step (2) is a step of preparing a surfactant-supporting granule group by spray drying the slurry obtained in step (1).

  The slurry atomization device may be a pressure spray nozzle, a two-fluid spray nozzle, or a rotating disk type, but the pressure spray nozzle is particularly preferable because the average particle size of the obtained granule group is preferably 150 to 500 μm. . From the viewpoint of obtaining the thermal efficiency of the spray drying tower and good stability during continuous operation, the temperature of the high-temperature gas supplied to the spray drying tower (hereinafter referred to as the blast temperature) is preferably 150 to 300 ° C. Preferably it is 170-250 degreeC. The temperature of the gas discharged from the spray drying tower (hereinafter referred to as exhaust air temperature) is preferably 70 to 125 ° C, more preferably 80 to 115 ° C. As the spray-drying tower, a countercurrent tower is more preferable because thermal efficiency and particle strength of the granule group are improved.

3. Physical Properties of Surfactant-Supporting Granule Group The average particle size of the surfactant-supporting granule group obtained as described above is preferably 150 to 500 μm, more preferably 180 to 500 μm, from the viewpoint of the solubility of the detergent particle group. 300 μm. The bulk density of the surfactant-carrying granule group is preferably 400 to 1000 g / L, more preferably 500 to 800 g / L, from the viewpoint of obtaining a detergent particle group having a bulk density of 500 g / L or more. The particle strength of the surfactant-carrying granule group is such that when the liquid surfactant composition is added to the surfactant-carrying granule group, the surfactant-carrying granule group does not collapse and the resulting detergent From the viewpoint that the particle group has good disintegrability, it is preferably 5 to 200 MPa, more preferably 10 to 150 MPa, and still more preferably 15 to 100 MPa. The moisture content of the supporting granule is preferably 1 to 8% by weight, more preferably 1 to 5% by weight, from the viewpoint of the handleability of the supporting granule.

The internal structure of the surfactant-carrying granules of the present invention can be confirmed using a mercury porosimeter as the pore volume distribution of the surfactant-carrying granules. In the pore volume distribution (hereinafter referred to as pore volume distribution) per pore diameter inside the supporting granules measured with a mercury porosimeter (for example, “Pore Sizer 9320” manufactured by Shimadzu Corporation), the pore volume is more If it is larger, the carrying capacity of the liquid composition increases, and the smaller the pore diameter, the higher the ability (holding force) to hold the liquid composition once absorbed by capillary action. Therefore, when the pore volume is larger and the pore diameter is smaller, the carrying ability of the surfactant is increased, and a lot of liquid composition can be carried and the liquid composition can be prevented from smearing. Therefore, the surfactant-supporting granule group of the present invention suitable for supporting a liquid composition has a pore volume distribution mode diameter (a pore diameter having the largest pore volume in the obtained pore volume distribution). It is preferably 1.5 μm or less, more preferably 1.3 μm or less, still more preferably 1.1 μm or less, particularly preferably 1.0 μm or less, and particularly preferably 0.9 μm or less, and 0.8 μm or less. Particularly preferred.
Regarding the pore volume of the surfactant-carrying granule group of the present invention, the pore volume having a pore diameter of 0.01 to 4 μm is preferably 0.4 mL / g or more, more preferably 0.45 mL / g or more. 0.50 mL / g or more is more preferable.

4). Manufacturing method of detergent particle group The detergent particle group of the present invention comprises 1 to 100 parts by weight of a surfactant composition with respect to 100 parts by weight of the above-mentioned surfactant-carrying granules, and the average particle size is 150 to 150 parts by weight. 750 μm and bulk density of 500 g / L or more. A suitable production method for obtaining such a detergent particle group includes the following step (3), and may further include a step (4) as necessary.
Step (3): A step of mixing the surfactant-supporting granule group with the surfactant composition in a liquid state.
Step (4): A step of mixing the mixture and fine powder and coating the surface of the mixture with the fine powder.

  Examples of the surfactant composition that can be used in the step (3) include one or more surfactants, preferably an anionic surfactant and a nonionic surfactant. Among these, a nonionic surfactant (D) having a melting point at 30 ° C. or lower and its immobilizing agent (F), and an anionic surfactant (E) having a sulfate group or a sulfonate group as necessary are contained. A surfactant composition is preferred. When the liquid surfactant composition contains an unneutralized product of the component (E) and the component (F), in the powder raw material other than the particles for supporting the surfactant or the particles for supporting The mixture may be neutralized by containing an alkali component such as potassium carbonate.

  The mixer used in step (3) is preferably, for example, a nozzle for adding a liquid surfactant composition or a jacket provided for controlling the temperature in the mixer. A suitable mixing time (in the case of batch type) and an average residence time (in the case of continuous type) are preferably, for example, 1 to 20 minutes, and more preferably 2 to 10 minutes. When the surfactant composition and the surfactant-carrying granule group are batch-type, the surfactant-carrying granule group is previously charged in the mixing apparatus and then the liquid surfactant composition is added. It is preferable to spray and supply the liquid surfactant composition. At that time, other powder raw materials may be used with less than 150 parts by weight, preferably less than 100 parts by weight, with respect to 100 parts by weight of the surfactant-supporting granules. The other powder raw material is preferably an aluminosilicate, inorganic powder such as a silicate compound such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound, The average particle diameter of metal soap or sodium carbonate is preferably 0.1 to 300 μm, more preferably 5 to 250 μm. The temperature of the surfactant composition to be mixed is preferably 10 ° C. or more of the pour point of the surfactant composition, more preferably 20 ° C. or more of the pour point from the viewpoint of ease of handling. In addition, from the viewpoint of thermal stability of the surfactant composition, it is preferably 95 ° C. or lower, and more preferably 90 ° C. or lower.

  Specific examples of preferable mixing apparatuses include the following. When performing by a batch type, the thing of (i)-(iii) is preferable. (B) Henschel mixer (Mitsui Miike Chemical Co., Ltd.), High Speed Mixer (Fukae Kogyo Co., Ltd.), Vertical Granulator (Powrec Co., Ltd.), Redige Mixer (Matsuzaka Giken Co., Ltd.) , Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), (b) Ribbon mixer (manufactured by Hiwa Machine Industry Co., Ltd.), (c) Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), and the like. Among the above mixers, more preferred are a Redige mixer and a Proshare mixer. Further, the surfactant-supporting granule group and the surfactant may be mixed using the continuous apparatus of the above mixer. Moreover, as a continuous type apparatus of a mixer other than the above, there are a flexo-mix type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.), and the like.

  Further, by performing the step (4), the fluidity and caking resistance of the detergent particles can be improved. Further, when the mixture obtained in the step (3) is not in a powder form, the step (4) includes a step of crushing the mixture using the fine powder as an auxiliary agent. In this case, the fine powder preferably has an average primary particle diameter of 0.1 to 10 μm from the viewpoint of improving the coverage of the detergent particles, and improving the fluidity and caking resistance of the detergent particles. The average particle diameter is measured by a method using light scattering (for example, a particle analyzer (manufactured by Horiba, Ltd.)) or SEM observation. As the fine powder, an aluminosilicate is desirable, and inorganic fine powder such as silicate compounds such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds, and primary particles are 0.00. A 1 to 10 μm metal soap can also be used. In addition, it is preferable in terms of detergency that the fine powder has high ion exchange ability and high alkali ability. The amount of 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 in terms of fluidity and usability. Parts by weight.

  The mixer used in the step (4) preferably has a crushing blade rotating at high speed in the mixer, for example, from the viewpoint of improving the dispersibility of the fine powder to be added and improving the crushing efficiency. It is also possible to carry out with the same apparatus. Further, the temperature in the mixer may be arbitrarily set according to the purpose, but a surfactant composition containing (D) component, (F) component, and optionally (E) component as a liquid surfactant. When used, if the penetration hardness of the surfactant composition is in the temperature range of 10 kPa or more, it is advantageous from the viewpoint of reducing the amount of fine powder added and improving the crushing efficiency.

5. Composition and physical properties of detergent particle group The blending amount of the component (E) in the detergent particle group of the present invention is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, with respect to 100 parts by weight of the component (D). Particularly preferred is 30 to 180 parts by weight. The amount of component (F) is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of component (D). In this range, the surfactant composition has a temperature range in which the viscosity is 10 Pa · s or less at a temperature equal to or higher than the pour point of the surfactant composition, and from the pour point of the surfactant composition. In the temperature range lower than the melting point of component (D), the surfactant composition has a temperature range in which the penetration hardness of the surfactant composition is 10 kPa or more. When added to the granule group, the surfactant composition is in a liquid state, and solidifies as a detergent particle group during storage to avoid deterioration of quality such as stains. The term “liquid” as used herein means a state having fluidity (a state at or above the pour point measured by the method defined in JIS K2269), and includes a paste form. The melting point is measured using a Mettler FP81 (manufactured by Mettler Instrumente AG) of an FP800 thermosystem at a heating rate of 0.2 ° C./min. Viscosity was measured using a B-type viscometer (DVM-B manufactured by TOKYOKIKI), rotor No. 3. It can be determined by measuring at a rotational speed of 12 r / min. The penetration hardness is a rheometer (NRM-3002D, manufactured by Fudo Kogyo Co., Ltd.) and a circular adapter (No. 3, 8φ) having a diameter of 8 mm and a bottom area of 0.5 cm ^2. The adapter is placed inside the surfactant composition. It can be determined as a value obtained by dividing the load when entering 20 mm at an approach speed of 20 mm / min by the bottom area of the circular adapter.

  The component (D) has a melting point of 30 ° C. or lower, preferably 25 ° C. or lower, particularly preferably 22 ° C. or lower. For example, polyoxyalkylene alkyl (phenyl) ether, alkyl (polyalkylene) polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxyalkylene alkylol (fatty acid) Amides are exemplified as preferred. Two or more of these nonionic surfactants may be used in combination. The nonionic surfactant may be used as an aqueous solution.

  Examples of the component (E) include sulfuric acid ester salts of alcohols having 10 to 18 carbon atoms, sulfuric acid ester salts of alcohol ethoxylates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α- Sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts and the like are preferable.

  Examples of the component (F) include anionic surfactants having a carboxylic acid group or a phosphoric acid group (excluding those having a sulfuric acid group or a sulfonic acid group). Specifically, fatty acid salts, hydroxy Examples include anionic surfactants such as fatty acid salts and alkyl phosphates. In particular, at least one member selected from amine salts such as sodium or potassium alkali metal salts of C10-22 fatty acids or hydroxy fatty acids, alkanolamines, and the like is preferable from the viewpoint of solubility. Examples of the component (F) include compounds having a melting point of 35 ° C. or higher and compatibility with the component (D). For example, 1 or more types chosen from the polyoxyalkylene type nonionic compound whose molecular weight is 3000-30000, the polyether type nonionic compound whose molecular weight is 3000-30000, etc. are mentioned. Particularly preferred examples include polyethylene glycol, polypropylene glycol, and polyoxyethylene alkyl ether having a melting point of 35 ° C. or higher. Here, the term “compatible” refers to a property in which the mixture of the component (D) is well mixed at any temperature equal to or higher than the melting point of the component (D) and phase separation is difficult. (F) You may mix and use these as a component.

  The amount of the liquid surfactant composition added is preferably 1 to 100 parts by weight, more preferably 10 to 100 parts by weight, and still more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the surfactant-supporting granules. Parts, particularly preferably 30 to 60 parts by weight. In addition, when adding the surfactant composition to the surfactant-carrying granule group, powder raw materials other than the surfactant-carrying granule group may be added if desired. 0-30 weight part is preferable with respect to 100 weight part of granule groups for surfactant carrying | support.

  Preferred physical properties of the detergent particles according to the present invention are as follows. The average particle diameter is more preferably 150 to 500 μm, still more preferably 180 to 350 μm. The bulk density is more preferably 500 to 1000 g / L, still more preferably 600 to 1000 g / L, and particularly preferably 650 to 850 g / L. The caking resistance is preferably 90% or more, more preferably 95% or more, with a sieve passing rate of 90% or more.

  Moreover, it is preferable that a detergent particle group is a mononuclear detergent particle group from a viewpoint of improving the solubility of detergent particle | grains and expressing the function of a washing | cleaning component at an early stage. “Mononuclear detergent particle group” means a detergent particle group containing mononuclear detergent particles. “Mononuclear detergent particles” are detergent particles in which a surfactant composition is supported on a group of particles for supporting a surfactant, and one surfactant particle is supported on one detergent particle. Detergent particles having granules as cores.

As a factor expressing mononuclearity, the grain growth degree defined by the formula [2] can be used, and the preferred grain growth degree is 0.75 to 1.5, more preferably 0.8 to 1.4. More preferably, it is 0.85-1.3, Most preferably, it is 0.9-1.2, Most preferably, it is 0.95-1.1.
Grain growth rate =
(Average particle diameter of final detergent particle group) / (Average particle diameter of granule group for supporting surfactant) [2]
The final detergent particle group means a detergent particle group in which a surfactant composition is supported on a surfactant-supporting granule group and subjected to surface modification treatment.

  As an example of the method for confirming the mononuclearity of the detergent particles, the mononuclearity can be confirmed by at least one of the following methods (a), (b), and (c). (A) Method: A detergent by cutting detergent particles arbitrarily sampled from around the average particle diameter of the detergent particles, and observing the presence / absence and the number of granules in the detergent particles with a scanning electron microscope (SEM) A method of confirming mononuclearity of particles. Method (b): An organic solvent that does not dissolve the water-soluble polymer in the support granules in the detergent particles (for example, polyacrylate as the water-soluble polymer in the support granules, and an anionic surfactant as the surfactant) (In the presence of LAS) or a nonionic surfactant, ethanol can be used preferably), and the organic solvent-soluble component in the detergent particles is extracted, and the subsequent organic solvent-insoluble component is observed by SEM observation. how to. That is, when one supporting granule is present in the organic solvent insoluble matter obtained by treating one detergent particle with the organic solvent, it is understood that the detergent particle is mononuclear. (C) Method: The detergent particles are separated by detecting the two-dimensional element distribution on the cut surface of the detergent particles encapsulated with resin with an energy dispersive X-ray spectrometer (EDS) or an electron beam microanalyzer (EPMA). How to check nuclearity.

6). Measuring Method of Physical Properties of Surfactant-Supporting Granule Group and Detergent Particle Group The physical property values of the surfactant-supporting granule group and the detergent particle group can be measured by the following method.

  1) Average particle diameter: It can be measured from the weight distribution according to the size of each sieve after vibrating for 5 minutes using a standard sieve defined in JIS Z 8801.

  2) Bulk density: It can be measured by the method defined in JIS K 3362.

  3) Particle strength: 20 g of sample was placed in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikagaku Co., Ltd., TVP1 tapping type densely packed bulk density meter, tapping conditions; period 36 The sample height (initial sample height) at that time is measured. Thereafter, the entire upper end surface of the sample held in the container by a pressure tester is pressurized at a speed of 10 mm / min, and a load-displacement curve is measured, and the slope of the linear portion with a displacement rate of 5% or less is obtained. The value obtained by multiplying the initial sample height and dividing by the pressurized area is taken as the particle strength.

  4) Moisture content: The moisture content of the granules is measured by the infrared moisture meter method. That is, 3 g of a sample is placed on a sample pan having a known weight, and the sample is heated and dried for 3 minutes by an infrared moisture meter (manufactured by Kett Science Laboratory Co., Ltd. (infrared lamp 185W)). After drying, weigh the sample pan and dry sample. The difference in weight between the container before and after drying obtained by the above operation and the weight of the sample is divided by the amount of the sample weighed and multiplied by 100 to calculate the amount of water in the sample.

5) Caking resistance: length × width × height = 10 cm × 6 cm × 4 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. 100 g of a sample is put in this box, and a total weight of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. The determination is performed by obtaining the passage rate as follows. The higher the pass rate, the higher the caking resistance, which is a preferable physical property as a detergent particle group.
<Screen passing rate>
The sample after the test is gently opened on a sieve (mesh opening 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the passage rate (%) with respect to the sample after the test is obtained.

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

6) Peak pore diameter (mode diameter)
The pore volume distribution of the granule for supporting a surfactant of the present invention can be measured using a mercury porosimeter (“Pore Sizer 9320” manufactured by Shimadzu Corporation).

7) Pore Volume The pore volume of the surfactant-supporting granule group is measured using “SHIMADZU Pore Sizer 9320” manufactured by Shimadzu Corporation and based on the instruction manual as follows. That is, the surfactant-supporting granule group is put in a cell, and the mercury to be injected is measured by dividing it into a low pressure part (0 to 14.2 psia) and a high pressure part (14.2 to 30000 psia). Measurement data is smoothed by taking a moving average of two pieces of data before and after, and a mode diameter in a range of 0.01 to 4 μm and a pore volume of 0.01 to 4 μm are obtained.

8) Necessary zeolite amount Necessary modified zeolite amount is the flowability of the manufactured detergent particles and the crystalline aluminosilicate having the lowest value (for example, product name “VALFOR100” manufactured by PQ Chemicals (Thailand)). The amount of addition. That is, the amount of aluminosilicate added when 100 parts by weight of the surfactant-supporting granule group is taken as 100% is shown.

7). Detergent Composition The detergent composition according to the present invention is a composition comprising the above-described detergent particle group, and further includes detergent components (for example, builder granules, fluorescent dyes, enzymes, A fragrance, an antifoaming agent, a bleaching agent, a bleaching activator, etc.).

  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, 80% by weight or more, 100% by weight or less from the viewpoint of detergency. Is particularly preferred.

  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.

8). Manufacturing method of detergent composition The manufacturing method of a detergent composition does not have limitation in particular, For example, the method of mixing the said detergent particle group and the separately added detergent component is mentioned. The detergent composition thus obtained contains a detergent particle group having a large amount of surfactant loaded, and therefore can exhibit a sufficient cleaning effect even with a small amount. The use of such a detergent composition is not particularly limited as long as it is a use using a powder detergent, and examples thereof include a powder detergent for clothing and a detergent for automatic tableware.

Example 1
Deionized water was added to a mixing tank having a stirring blade, and after the water temperature reached 55 ° C., sodium sulfate (“anhydrous neutral sodium sulfate”, manufactured by Shikoku Kasei Co., Ltd.) was added and stirred for 10 minutes. Furthermore, sodium carbonate (“Dense Ash”, manufactured by Central Glass Co., Ltd.), sodium sulfite (sodium sulfite, manufactured by Mitsui Chemicals), sodium alkyl sulfate (“Emar 10 Powder”, manufactured by Kao Corporation) as a surfactant ) Was added and stirred for 10 minutes. Then 40% by weight aqueous sodium polyacrylate solution was added. After further stirring for 10 minutes, crystalline aluminosilicate (manufactured by PQ Chemicals (Thailand), trade name “VALFOR100”) and sodium chloride were added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C. This slurry was spray-dried to obtain a granule group for supporting a surfactant. Table 1 shows the composition and physical properties of the surfactant-supporting granules. In the table, "soda ash" is sodium carbonate, "sodium silicate" is sodium sulfate, "sulfite" is sodium sulfite, "zeolite" is crystalline aluminosilicate, and "oligomer D" is 40 wt% polyacrylic. An aqueous sodium acid solution (weight average molecular weight 10,000, manufactured by Kao Corporation) is shown.

  Next, 47 parts by weight of the obtained granules for supporting a surfactant and 6.5 parts by weight of crystalline silicate (“Prefeed”, manufactured by Tokuyama Siltech Co., Ltd.) were used as a Redige mixer (Matsusaka Giken Co., Ltd.). Manufactured, with a capacity of 20 L, with a jacket), and stirred for 1 minute at a spindle of 80 rpm. Subsequently, the following liquid surfactant composition was added in 1 minute, and after stirring for 7 minutes at 60 rpm, 4 parts by weight of crystalline silicate was added and stirred for 20 seconds at 150 rpm and chopper 4000 rpm. Was done. Subsequently, 4 to 13 parts by weight of crystalline aluminosilicate (manufactured by PQ Chemicals (Thailand), trade name “VALFOR100”) is added, and surface modification is performed for 40 seconds at a main shaft of 150 rpm and a chopper of 4000 rpm, and a detergent particle group Got. The required amount of modified zeolite was 6 parts by weight. Table 1 shows the physical properties of the obtained detergent particles.

  The liquid surfactant composition is composed of 13 parts by weight of polyoxyethylene alkyl ether (“Emulgen 108KM”, EO 8.5, manufactured by Kao Corporation), polyethylene glycol (“K-PEG 6000”, weight average molecular weight 8500, Kao). (Made by Co., Ltd.) 5 parts by weight, palmitic acid corresponding to 0.5 parts by weight sodium palmitate ("Lunac P-95", manufactured by Kao Corporation) and LAS precursor corresponding to 15 parts by weight LAS-Na ("Neopelex FS") Manufactured by Kao Corporation), and a sodium hydroxide aqueous solution as a neutralizing agent was mixed at 80 ° C.

Examples 2-5 and Comparative Examples 1-4
A slurry for a surfactant-carrying granule group was prepared so as to have the composition shown in Tables 1 and 2, and a surfactant-carrying granule group was prepared in the same manner as in Example 1. The physical properties of the obtained granules for supporting a surfactant are shown in Tables 1-2. For surfactants, the following were used:
Examples 2 and 3: Same as Example 1.
Example 4: A 30% by weight sodium alkylsulfate aqueous solution, "Emar 10 Powder" manufactured by Kao Corporation, dissolved in ion-exchanged water.
Example 5: 30% by weight of polyoxyethylene alkyl ether sodium sulfate aqueous solution [Kao Co., Ltd. “Emar 227-pH 11”, average added mole number: 2 mol].
Comparative Example 2: Polyoxyethylene alkyl ether, “Emulgen 108KM” manufactured by Kao Corporation, EO addition mole number: 8.5
Comparative Example 3: Polyethylene glycol, manufactured by Kao Corporation, “K-PEG6000”, average molecular weight 8500
Comparative Example 4: 40 wt% aqueous sodium alkylbenzene sulfonate solution.

  The slurry for the surfactant-supporting granule group was prepared by blending the components in the order shown in Table 3.

  Next, a detergent particle group was obtained in the same manner as in Example 1 except that the obtained surfactant-carrying granule group was used. The physical properties of the obtained detergent particles are shown in Tables 1-2.

  From the results of Tables 1 and 2, the detergent particle groups obtained using the surfactant-carrying granule groups obtained in Examples 1 to 5 are all compared to those obtained in Comparative Examples 1 to 4. It can be seen that even if the amount of the required modified zeolite is low, the fluidity is excellent.

  The surfactant-supporting granule group of the present invention can be blended in a detergent composition suitably used for a powder detergent for clothing, a detergent for automatic tableware and the like.

Claims (10)

A surfactant-supporting granule group obtained by spray-drying a slurry containing a water-soluble polymer, a water-soluble salt and a compound represented by the following formula [1], which is represented by the formula [1] A surfactant-supporting granule group, wherein the content of the compound in the surfactant-supporting granule group is 0.001 to 3% by weight .
R—O (CH ₂ CH ₂ O) n—SO ₃ M [1]
(In the formula, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, average added mole number n is 0 to 7, M represents Na, K, NH ₄ or triethanolammonium) Particles for supporting a surfactant according to claim 1 Symbol placement n is 0 in the compound represented by the formula (1). The granule group for supporting a surfactant according to claim 1 or 2, wherein the slurry further contains a water-insoluble inorganic substance. The surfactant-supporting granule group according to any one of claims 1 to 3 , wherein the compound represented by the formula [1] added to the slurry is a powder. Mode diameter of the pore volume distribution by mercury porosimetry is the 0.364~ 1. 0μ m, pore volume distribution of the pore diameter 0.01~4μm is 0.4 ~0.535 ml / g, particle strength The surfactant-supporting granule group according to any one of claims 1 to 4 , which has a viscosity of 15 to 100 MPa. A method for producing a surfactant-supporting granule group comprising a step of spray-drying a slurry containing a water-soluble polymer, a water-soluble salt and a compound represented by the following formula [1], which is represented by the formula [1] A method for producing a surfactant-supporting granule group, wherein the content of the compound in the surfactant-supporting granule group is 0.001 to 3% by weight .
R—O (CH ₂ CH ₂ O) n—SO ₃ M [1]
(In the formula, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents 0 to 7, M represents Na, K, NH ₄ or triethanolammonium). The method for producing a surfactant-supporting granule group according to claim 6 , wherein a slurry is prepared by mixing a liquid containing a water-soluble polymer and a water-soluble salt and a compound represented by the formula [1]. A detergent particle group in which 1 to 100 parts by weight of a surfactant composition is supported on 100 parts by weight of the surfactant-supporting granules according to any one of claims 1 to 5 , wherein the average particle size is 150 to 750 µm. And a detergent particle group having a bulk density of 500 g / L or more. The detergent particle group according to claim 8 , wherein the detergent particle group is mononuclear. A detergent composition comprising the detergent particle group according to claim 8 or 9 .