WO2012033006A1

WO2012033006A1 - Method for producing detergent particle group

Info

Publication number: WO2012033006A1
Application number: PCT/JP2011/069978
Authority: WO
Inventors: 窪田輝夫
Original assignee: 花王株式会社
Priority date: 2010-09-06
Filing date: 2011-09-02
Publication date: 2012-03-15
Also published as: CN103108947B; TW201211237A; JP2012056984A; CN103108947A; JP5631127B2; TWI493029B

Abstract

The invention is a method for producing a detergent particle group, comprising: a step (A) of preparing base granules in which the contents of sodium carbonate, a water-insoluble inorganic salt, an acrylic acid-based polymer, and a surfactant fall within specific ranges, respectively, by spray-drying a slurry containing sodium carbonate, an acrylic acid-based polymer in which the ratio of the constituent unit of acrylic acid or a salt thereof to the total monomer constituent units constituting the polymer is from 90 to 100% by mole, and water, and optionally containing a water-insoluble inorganic salt; a step (B) of preparing a surfactant composition containing a surfactant including a predetermined amount of a nonionic surfactant and water in amounts within specific ranges; and a step (C) of mixing the base granules obtained in the step (A) and the surfactant composition obtained in the step (B) while substantially maintaining the form of the base granules.

Description

Method for producing detergent particles

The present invention relates to a method for producing detergent particles.
Background art

The fluidity of the detergent particles constituting the powder detergent is an important physical property from the viewpoints of improvement in productivity and ease of use, and there is a demand for detergent particles with high fluidity. Here, the fluidity is, for example, the time required for 100 ml of powder to flow down in a bulk density measuring device defined in JIS K3362. If the fluidity is high, the time required for filling the detergent can be shortened, so that the productivity is improved.

In general, in powder detergents for clothing, surfactants are mainly formulated with an anionic surfactant as the main component, and various improvements in fluidity in such a blended system have been proposed. WO-A 2006/013982 (corresponding to JP-A 2006-137925 and EP-A 1788071) was obtained by mixing a surfactant composition containing water and a specific anionic surfactant with base granules. A method for producing a mononuclear detergent particle group in which a mixture is surface-modified with a fine powder is disclosed. WO-A 2005/083049 (corresponding to JP-A 2007-522330) is a three-way cleaning of an anionic detersive surfactant, a nonionic detersive surfactant, and a cationic detersive surfactant. Granular laundry detergent compositions are disclosed that contain a surfactant system and contain little or no zeolite builders and phosphate builders. Further, as prior art relating to detergent particles obtained by loading a base granule with a surfactant and a method for producing the same, WO-A99 / 029830 (corresponding to EP-A0996982) and WO-A00 / 023560 (EP- (Corresponding to A1041139)
Summary of invention

The present invention relates to a method for producing detergent particles, comprising the following steps (A) to (C).
Step (A): Sodium carbonate, an acrylic acid type polymer in which the proportion of the constituent units of acrylic acid or a salt thereof with respect to all monomer constituent units constituting the polymer is 90 to 100 mol%, and water, A slurry that may contain an insoluble inorganic salt is spray-dried, and contains 25 to 80% by mass of sodium carbonate, 0 to 30% by mass of a water-insoluble inorganic salt, and 2 to 25% by mass of an acrylic acid type polymer, and has surface activity. A step of preparing a base granule having an agent content of 2% by mass or less,
Step (B): a step of preparing a surfactant composition containing a total of 50 to 80% by weight of the surfactant, 15% by weight or more of the nonionic surfactant and 20 to 50% by weight of water,
Step (C): A step of mixing the base granule obtained in the step (A) and the surfactant composition obtained in the step (B) while substantially maintaining the form of the base granule.

Furthermore, the present invention relates to a method for producing detergent particles comprising the following steps (A) to (C).
Step (A): A slurry containing sodium carbonate, polyacrylic acid or a salt thereof, and water, which may contain a water-insoluble inorganic salt, is spray-dried to obtain 25 to 80% by mass of sodium carbonate, a water-insoluble inorganic salt. A step of preparing a base granule containing 0 to 30% by mass and 2 to 25% by mass of polyacrylic acid or a salt thereof and having a surfactant content of 2% by mass or less;
Step (B): a step of preparing a surfactant composition containing a total of 50 to 80% by weight of the surfactant, 15% by weight or more of the nonionic surfactant and 20 to 50% by weight of water,
Step (C): A step of mixing the base granule obtained in the step (A) and the surfactant composition obtained in the step (B) while substantially maintaining the form of the base granule.
Furthermore, the present invention provides a detergent particle group obtained by the above production method, a method of washing a textile product using the detergent particle group obtained by the above production method, or a fiber of the detergent particle group obtained by the above production method. Provide use for product cleaning.
Detailed Description of the Invention

Conventionally, in order to improve the fluidity of a powder detergent, a method of modifying the surface by coating the surface of the detergent particles with a water-insoluble inorganic powder such as zeolite is generally performed. However, when a highly liquid surfactant such as a nonionic surfactant is blended as the surfactant, it becomes difficult to produce a detergent particle group having excellent fluidity as the surfactant content increases. As a countermeasure, in addition to the previous surface modification, a method has been proposed in which, for example, an oil-absorbing carrier such as amorphous silica or porous spray-dried particles is used to increase the oil-absorbing ability and adjust the powder physical properties. However, in order to increase the yield in production, there is a demand for more fluid detergent particles.

The present invention provides a method capable of producing a detergent particle group excellent in fluidity with a high yield, particularly a method capable of producing a detergent particle group containing a nonionic surfactant with a high yield.

The present inventor has conducted various studies on methods for obtaining a powder detergent particle group having excellent fluidity, and found that a powder detergent particle group having excellent fluidity can be obtained by a very simple production method, thereby increasing production efficiency. As a result, the present invention was useful as a final product.

According to the present invention, there is provided a method capable of producing a detergent particle group excellent in fluidity. Furthermore, the present invention also provides a method for producing detergent particles having excellent fluidity even when the blending amount of water-insoluble inorganic salts conventionally used as surface modifiers such as zeolite is reduced. is there. In addition, the present invention does not require a surface modification step, and produces a detergent particle group having excellent fluidity.

<Process (A)>
In the production method of the present invention, the step (A) is an acrylic acid type polymer in which the proportion of the structural unit of acrylic acid or a salt thereof is 90 to 100 mol% with respect to all the monomer structural units constituting sodium carbonate and the polymer Preferably, the slurry containing polyacrylic acid or a salt thereof and water, which may contain a water-insoluble inorganic salt, is spray-dried to obtain 25-80% by mass of sodium carbonate, 0-30% by mass of the water-insoluble inorganic salt And a base granule containing 2 to 25% by mass of polyacrylic acid or a salt thereof and having a surfactant content of 2% by mass or less.

“Water-insoluble” with respect to the water-insoluble inorganic salt used in the step (A) means that the amount dissolved in 100 g of ion-exchanged water at 20 ° C. is 1 g or less.

In the present invention, the water-insoluble inorganic salt preferably has an average primary particle size of 0.1 to 20 μm. For example, crystalline or amorphous aluminosilicate, silicon dioxide, hydrated silicate compound, Although there are clay compounds such as pearlite and bentonite, crystalline or amorphous aluminosilicates, silicon dioxide and hydrated silicate compounds are preferred, and crystalline aluminosilicates are particularly preferred. Among water-insoluble inorganic salts, zeolite known as crystalline aluminosilicate is compounded as a sequestering agent, and clay compound is blended as a flexible substrate. In addition, by including a water-insoluble inorganic salt in the base granule, the final density of the finally obtained detergent particles can be increased, and the particle strength can be increased. May be a constituent. However, according to the production method of the present invention, even if the ratio of the water-insoluble inorganic salt in the base granule is limited, excellent fluidity can be obtained with little influence on strength reduction.

The acrylic acid type polymer of the present invention is a structural unit in which the main structural unit constituting the polymer is derived from a monomer of acrylic acid or a salt thereof. Therefore, the acrylic acid type polymer can also be expressed as an acrylic acid homopolymer, an acrylic acid copolymer, or a salt thereof. In the present invention, the proportion of the constituent units from the acrylic acid monomer in the monomer constituent units of the acrylic acid type polymer is 90 to 100 mol%. The proportion of acrylic acid monomer constituent units in the monomer constituent units of the acrylic acid type polymer is preferably 95 to 100 mol%, more preferably 97 to 100 mol%, and the proportion is 100 mol% of polyacrylic acid (A homopolymer of acrylic acid) is even more preferable. The acrylic acid type polymer may be a salt of an alkali metal or the like. By using an acrylic acid type polymer containing a large amount of acrylic acid or a salt thereof as a monomer constituent unit of the polymer, a detergent particle group having excellent powder physical properties can be obtained.

The monomer constituent unit other than the constituent unit of acrylic acid or a salt thereof constituting the acrylic acid type polymer is a constituent unit derived from a monomer copolymerizable with acrylic acid or a salt thereof, and the effect of the present invention is impaired. First, one that does not modify the carboxylic acid group of acrylic acid is selected. As a monomer other than acrylic acid or a salt thereof for constituting the acrylic acid type polymer, a nonionic monomer and / or an anionic monomer, and further an anionic monomer are preferable. Specific examples of anionic monomers include sulfonic acid monomers such as allyl sulfonic acid, vinyl sulfonic acid, and methallyl sulfonic acid, and carboxylic acid monomers other than acrylic acid such as maleic acid, methacrylic acid, and itaconic acid. Can be mentioned. Furthermore, the acrylic acid type copolymer of the present invention is preferably an acrylic acid copolymer which is a copolymer of acrylic acid and allylsulfonic acid or maleic acid or a salt of the copolymer. In particular, the acrylic acid type polymer of the present invention is preferably polyacrylic acid or a salt thereof which is a homopolymer of acrylic acid.
As the acrylic acid type polymer, preferably polyacrylic acid or a salt thereof, those having a weight average molecular weight of 100 to 80,000, more than 2000 and having 10 or more carboxyl groups are more preferable. Accordingly, the weight average molecular weight of the acrylic acid type polymer, preferably polyacrylic acid or a salt thereof is preferably 2000 to 80000. The salt of acrylic acid type polymer, preferably polyacrylic acid is preferably an alkali metal salt, more preferably a sodium salt. You may mix | blend with the slurry for spray-drying as an acid or a partially neutralized material, and you may neutralize in a slurry. The weight average molecular weight can be measured by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance.

The base granule is prepared by spray drying a slurry containing sodium carbonate, an acrylic acid type polymer, preferably polyacrylic acid or a salt thereof, and water, and optionally a water-insoluble inorganic salt.

In addition to these components, for example, builders generally used in garment detergents, for example, sequestering agents such as citrate and sodium tripolyphosphate, alkaline agents such as potassium carbonate and alkali metal silicate, crystals One or more of base materials having both sequestering ability and alkaline ability such as basic silicates and / or other bases generally used in detergent compositions, for example, known in the field of detergents for clothing Surfactants, acrylic acid maleic acid copolymers other than the above-mentioned acrylic acid type polymers, anti-contamination agents such as carboxymethyl cellulose, inorganic powders such as sodium sulfate, sodium sulfite, and sodium chloride, fluorescent whitening agents, and fragrances. Can be blended. However, the base granule preferably has a phosphate builder content of 5% by mass or less, and more preferably contains substantially no phosphate builder.

When the base granule contains a crystalline aluminosilicate such as zeolite as a water-insoluble inorganic salt, the water content in the base granule after spray drying is 12 mass in the base granule from the viewpoint of increasing the action of adsorbing the water of the zeolite. % Or less is preferable, 6 mass% or less is more preferable, and 3 mass% or less is still more preferable.
The conditions (temperature, spray drying apparatus, spraying method, drying method, etc.) for spray drying the slurry for preparing the base granule may be any known method, and are not particularly limited.

The base granule obtained in step (A) is 25 to 80% by weight of sodium carbonate, preferably 30 to 75% by weight, more preferably 45 to 70% by weight, and 0 to 30% by weight of water-insoluble inorganic salt, preferably An acrylic acid type polymer in which the proportion of the constituent units of acrylic acid or a salt thereof is 90 to 100% by mass, more preferably 0 to 5% by mass, more preferably 0 to 5% by mass, The polyacrylic acid or a salt thereof is preferably contained in an amount of 2 to 25% by mass, preferably 3 to 20% by mass, more preferably 6 to 15% by mass. The surfactant content is 2% by mass or less, preferably 1% by mass or less, and more preferably 0.1% by mass. This range is preferable from the viewpoint of obtaining a detergent particle group excellent in fluidity. In addition, the remainder of the base granule excluding water is preferably an alkali metal sulfate or alkali metal sulfite, and more preferably sodium sulfate. Specifically, in addition to each component and concentration range (which may be a preferable concentration range) of the base granule, the content of alkali metal sulfate is preferably 10 to 40% by mass in the base granule, The content of alkali metal sulfite is preferably 0 to 2% by mass in the base granule.

The pore volume of the base granule produced in the cocoon step (A) is preferably 0.2 mL / 1 g or more, more preferably 0.3 mL / 1 g or more. The average pore diameter is preferably 1 μm or less, more preferably 0.8 μm or less. Within this range, aggregation of the base granules is suppressed, which is suitable for maintaining the mononuclearity of the particles in the detergent particle group. The measuring method of the pore volume and the average pore diameter is as follows.

Measured from the distribution of pore volume per pore diameter inside the base granule measured by a mercury porosimeter (“SHIMADZU pore sizer 9320” manufactured by Shimadzu Corporation). The pore volume is in the range of 0.01 μm to 4 μm. It is a certain pore volume, and the average pore diameter means the mode diameter of the pore volume distribution (the pore diameter having the largest pore volume in the obtained pore volume distribution).

The particle strength is preferably 50 to 2000 kg / cm ² , more preferably 100 to 1500 kg / cm ² , and particularly preferably 150 to 1000 kg / cm ² . Within this range, the base granule group exhibits good disintegration properties, and a detergent particle group having good high-speed solubility can be obtained. The method for measuring the particle strength is as follows.

20 g of sample is put into a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapping 30 times (Tsutsui Rikenki Co., Ltd., TVP1 type tapping type close-packed dense density measuring instrument, tapping condition; period 36 times / min, 60 mm The sample height at that time (initial sample height) is measured. Thereafter, the entire upper end surface of the sample held in the container with 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.

The bulk density of the base granule is preferably 200 to 900 g / L, more preferably 300 to 800 g / L, still more preferably 350 to 700 g / L, and particularly preferably 400 to 600 g / L. The bulk density is measured by a method defined by JIS K K 3362: 2008.

The average particle size of the base granule is preferably 150 to 500 μm, more preferably 180 to 300 μm. The average particle size is determined by shaking the mass for 5 minutes using a standard sieve of JIS Z 8801: 2006 (mesh opening 2000-125 μm, see Appendix Tables 1 and 2 of JIS K 3622: 2008), The median diameter is calculated from the rate.

<Process (B)>
In the production method of the present invention, the step (B) comprises a surfactant composition containing a total of 50 to 80% by weight of the surfactant, 15% by weight or more of the nonionic surfactant and 20 to 50% by weight of water. Is a step of preparing

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and nonionic surfactants and anionic surfactants are preferred.

As the nonionic surfactant, a nonionic surfactant having a melting point at 30 ° C. or lower is preferable. The melting point of the nonionic surfactant is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and further preferably 22 ° C. or lower. Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, alkyl (polyoxyalkylene) polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene- Polyoxypropylene-polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene-block polymer, and polyoxyalkylene alkylol (fatty acid) amide are preferred. The alkyl group of the nonionic surfactant is preferably an alkyl group having 8 to 22 carbon atoms.

The nonionic surfactant is preferably a polyoxyalkylene alkyl ether having an alkyl group having 8 to 22 carbon atoms, and further having an alkyl group having 10 to 14 carbon atoms, and an average addition mole of an oxyalkylene group containing an oxyethylene group. Polyoxyalkylene alkyl ethers having a number of 4 to 25 mol, more preferably 4 to 21 mol, and further 4 to 12 mol are preferred. The oxyalkylene group other than the oxyethylene group is preferably an oxypropylene group. Among the average addition moles of oxyalkylene groups, those having an addition mole number of oxypropylene groups of 0 to 3 and an average addition mole number of oxyethylene groups of 4 to 22 are preferred. The addition order of the oxypropylene group and the oxyethylene group may be random or block.

As the nonionic surfactant of the present invention, a polyoxyalkylene alkyl ether obtained by adding 4 to 12 mol (preferably 6 to 10 mol) of alkylene oxide to an alcohol having 10 to 14 carbon atoms is preferable. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide, and ethylene oxide is preferable. More preferred nonionic surfactants are polyoxyethylene alkyl ethers in which the alkyl group has 10 to 14 carbon atoms, and the average added mole number of oxyethylene groups is 4 to 12 moles, more preferably 6 to 10 moles. .

In addition, from the viewpoint of solubility, particularly solubility at low temperatures, a compound obtained by subjecting such an alcohol to block polymerization or random polymerization of ethylene oxide, propylene oxide, and, if necessary, ethylene oxide is also preferable. Among these, EPE nonion is preferable. A nonionic surfactant may be used independently and may use 2 or more types together.

Note that the melting point of the nonionic surfactant is measured using a Mettler FP81 (manufactured by Mettler Instruments Inc. AG) of an FP800 thermosystem at a temperature rising rate of 0.2 ° C./min.

Examples of the anionic surfactant include sulfuric acid ester salts of alcohols having 10 to 18 carbon atoms, sulfuric acid ester salts of alkoxylated products of alcohols having 8 to 20 carbon atoms, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonic acids Salts, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, a linear alkylbenzene sulfonate having an alkyl chain with 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms is preferred, and alkali metals and amines are preferred as the counter ion, particularly sodium and / or Or potassium, monoethanolamine, and diethanolamine are preferable.

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

Examples of amphoteric surfactants include carbobetaine type and sulfobetaine type.

When the surfactant in step (B) contains both a nonionic surfactant and an anionic surfactant, the mass ratio of the nonionic surfactant / anionic surfactant is obtained by detergency and foaming. From the viewpoint of the fluidity of the detergent particles, 10/1 to 1/3 is preferable, 5/1 to 1/2 is more preferable, and 4/1 to 1/1 is still more preferable.

The content of the surfactant in the surfactant composition is 50 to 80% by mass, preferably 55 to 75% by mass, and in the surfactant concentration range, the nonionic interface in the surfactant composition The content of the activator is 15% by mass or more, and preferably 30% by mass or more. The water content in the surfactant composition is 20 to 50% by mass, preferably 25 to 45% by mass. The surfactant composition may contain components other than the surfactant and water, but the total content of the surfactant and water is 80 to 99.99% by mass, more preferably 90 to 99.9% by mass. % Is preferred.

In addition, when a fatty acid salt is blended as a surfactant, at least one selected from sodium and potassium salts of saturated fatty acids having 12 to 20 carbon atoms is preferable. The content of the fatty acid salt is preferably 0.5 to 10% by mass in the surfactant composition, more preferably 1 to 1% after satisfying the mass ratio of the nonionic surfactant / anionic surfactant. 7.5% by mass.

成分 As a component other than the surfactant and water, a nonionic compound having a polyoxyalkylene group (excluding the nonionic surfactant) may be contained. Examples of such nonionic compounds include (i) polyoxyalkylene having an oxyalkylene group having 2 to 5 carbon atoms and a weight average molecular weight of 3000 to 30000, and (ii) a weight average molecular weight of 3000 to 30000. And one or more compounds selected from polyoxyalkylene alkyl ethers (wherein the alkyl group has 1 to 4 carbon atoms). Particularly preferred examples of the nonionic compound include polyethylene glycol, polypropylene glycol, and polyoxyethylene methyl ether. The molecular weight of the nonionic compound can be measured in the same manner as the above acrylic acid type polymer, but if there is a problem in the measurement, it can be measured using the light scattering method, and dynamic light scattering can be performed. Measure using a photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.).

で By containing the fatty acid salt, polyethylene glycol, and the like, it is possible to more effectively improve the anti-bleeding and non-caking resistance of the nonionic surfactant.

<Process (C)>
In the production method of the present invention, in the step (C), the base granule obtained in the step (A) and the surfactant composition obtained in the step (B) are substantially converted into the form of the base granule. It is the process of mixing while maintaining. In the step (C), the surfactant composition and the base granule are uniformly mixed, whereby a detergent particle group having powder physical properties described later can be easily produced.

In the step (C), the mixing ratio of the surfactant composition and the base granule is preferably the surfactant composition with respect to 100 parts by mass of the base granule from the viewpoint of detergency and fluidity of the resulting detergent particles. The amount is 25 to 60 parts by mass, more preferably 30 to 55 parts by mass, and most preferably 35 to 50 parts by mass. In addition, the preferable requirements on the structure of the base granule and the surfactant composition, for example, the definition of preferable compounds and content, are effective in the mixing ratio of the step (C), and are also more preferable requirements.

The mixer for mixing the surfactant composition and the base granule used in the step (C) includes, for example, a nozzle for adding the surfactant composition and a jacket for controlling the temperature in the mixer. Those are preferred.

The mixing conditions in the cocoon step (C) are selected so that the morphology of the base granules is substantially maintained, i.e., does not collapse. For example, when using a mixer equipped with a stirring blade, from the viewpoint of suppressing the collapse of the water-soluble inorganic salt and from the viewpoint of mixing efficiency, if the shape of the mixing blade of the stirring blade provided in the machine is a paddle type, the stirring The fluid number of the blade is preferably 0.5 to 8, more preferably 0.8 to 4, and still more preferably 0.5 to 2. In the case where the shape of the mixing blade is a screw type, the fluid number of the stirring blade is preferably 0.1 to 4, more preferably 0.15 to 2. When the mixing blade has a ribbon shape, the fluid number of the stirring blade is preferably 0.05 to 4, more preferably 0.1 to 2.

Furthermore, you may use the mixer which comprises a stirring blade and a crushing blade. When mixing the base granule and the surfactant composition using such a mixer, it has conventionally been customary to rotate the crushing blade at a high speed in order to promote mixing. However, in the case of the present invention, it is preferable not to rotate the crushing blade substantially from the viewpoint of suppressing the collapse of the base granules. The fact that the crushing blade is not substantially rotated means that the crushing blade is not rotated at all, or in view of the shape, size, etc. of the crushing blade, the retention of various raw materials in the vicinity of the crushing blade is prevented within the range where the base granule is not collapsed. This means that the crushing blade is rotated for the purpose. Specifically, when the crushing blade is continuously rotated, the fluid number is preferably 200 or less, more preferably 100 or less, and when it is intermittently rotated, the fluid number is not particularly limited. By mixing under such conditions, a mixture can be obtained without substantially breaking the base granules.

In the present specification, the fact that the form of the base granule is not substantially maintained or collapsed means that 70% by number or more of the base granule maintains the form in the mixture. For example, a method of observing particles after extracting a soluble component of the obtained mixture using an organic solvent can be mentioned.

Further, the fluid number defined in this specification is calculated by the following equation.
Fluid number = V ² / (R × g)
Here, V: peripheral speed [m / s] at the tip of the stirring blade or crushing blade
R: Rotating radius of stirring blade or crushing blade [m]
g: Gravity acceleration [m / s ² ]

In the cocoon process (C), powder raw materials other than the base granules can be blended if desired. The blending amount is preferably 30 parts by mass or less, more preferably 15 parts by mass or less with respect to 100 parts by mass of the base granule from the viewpoint of solubility.

粉体 The powder raw material other than the base granule referred to in the present specification means a powder cleaning strength enhancer or oil absorbent at room temperature. Specifically, bases showing sequestering ability such as zeolite and citrate, bases showing alkaline ability such as sodium carbonate and potassium carbonate, sequestering ability and alkaline ability such as crystalline silicate Examples thereof include bases and the like, and amorphous silica, amorphous aluminosilicate, clay mineral and the like having low sequestering ability but high oil absorption ability. By using this powder raw material together with the base granule group as desired, it is possible to increase the surfactant composition and reduce the adhesion of the mixture into the mixer, and also to improve the cleaning power. .

At the same time as step (C) or after step (C), water-insoluble inorganic salts such as 0.1 to 20 μm water-insoluble inorganic salt zeolite, silica and clay minerals are added as fine powders, so that the water-insoluble Inorganic salts can be used as surface modifiers for detergent particles. Usually, the fluidity of the detergent particles can be improved by the surface modifier. This is particularly effective when a liquid surfactant such as a nonionic surfactant is used. However, in the present invention, excellent powder fluidity can be obtained even if these water-insoluble inorganic salts are intentionally reduced in the amount of the surface modifier or even if no surface modifier is used. That is, according to the production method of the present invention, even if the number of steps to be treated with the surface modifier is reduced or the treatment time is shortened in the production process, detergent particles having excellent fluidity can be obtained, and thus production efficiency is improved. . Furthermore, as a result, it is possible to obtain a powder detergent with excellent flowability, in which the surface modifier is reduced or substantially free of the surface modifier as a final product.

The detergent particle group of the present invention does not exclude the blending of these water-insoluble inorganic salts after the step (C), but the water-insoluble inorganic salt blended simultaneously with the step (C) or after the step (C) In the detergent particle group, it may be 5% by mass or less, and further 2% by mass or less, and in particular, excellent powder physical properties can be obtained even if not substantially contained as a surface modifier.

In addition, the temperature inside the apparatus at the time of mixing is preferably a temperature at which the surfactant composition and the base granule can be efficiently mixed while substantially suppressing the collapse of the base granule. For example, the pour point or higher of the surfactant composition to be mixed is preferable, the pour point of 10 ° C or higher is more preferable, and the pour point of 20 ° C or higher is particularly preferable. The mixing time is preferably about 2 to 10 minutes. The in-machine temperature can be adjusted by flowing cold water or hot water through a jacket or the like. Therefore, the apparatus used for mixing preferably has a structure with a jacket.

The mixing method of the surfactant composition and the base granule may be a batch type or a continuous type. When mixing batchwise, it is preferable to add the surfactant composition after the base granule is previously charged in the mixer. The temperature of the surfactant composition to be supplied is preferably 70 ° C. or less, more preferably 60 ° C. or less, from the viewpoint of the stability of the surfactant composition.

When mixing in a batch type, there is no particular limitation as long as a mixer generally used for batch type mixing is used. For example, the mixing blade shape is a paddle type mixer. A mixer having a shaft, and mixing the powder by attaching a stirring blade to the shaft: for example, Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granule Rator (Powrec Co., Ltd.), Redige Mixer (Matsubo Co., Ltd.), Proshear Mixer (Pacific Kiko Co., Ltd.), TSK-MTI Mixer (Tsukishima Kikai Co., Ltd.), JP 10-296064 (2) Cylindrical, semi-cylindrical, or conical fixed containers, such as mixing apparatuses described in Japanese Laid-Open Patent Publication No. 10-296065, etc. Mixers that mix by rotating ribbon-shaped blades that form spirals in the vessel: Ribbon mixer (manufactured by Hiyori Machinery Co., Ltd.), batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), ribocorn (3) As a mixer with screw-shaped mixing blades such as (made by Daishun Seisakusho Co., Ltd.), Julia mixer (manufactured by Tokuju Kogyo Co., Ltd.), (3) screw along the conical container is the wall of the container There are mixers that perform mixing by revolving while rotating around an axis parallel to the axis: for example, Nauter mixer (manufactured by Hosokawa Micron Corporation), SV mixer (manufactured by Shinko Pantech Co., Ltd.), and the like.

In addition, when mixing in a continuous mode, there is no particular limitation as long as a continuous mixer generally used for continuous mixing is used, but for example, the base granule and A surfactant composition may be mixed.

洗剤 Detergent particles can be obtained by the production method including the steps (A) to (C). In the detergent particle group produced according to the present invention, the content of the water-insoluble inorganic salt is preferably 5% by mass or less, and more preferably substantially free of the water-insoluble inorganic salt. The detergent particle group produced according to the present invention preferably has a phosphate builder content of 5% by mass or less, and more preferably contains substantially no phosphate builder. The present invention is suitable as a method for producing detergent particles for textiles such as clothing.

The individual detergent particles of the detergent particles produced according to the present invention are preferably mononuclear detergent particles. Here, the mononuclear detergent particles refer to detergent particles manufactured using base granules as a core, and substantially having one base granule as a core in one detergent particle.

In addition, the particle growth degree defined by the following formula can be used as an index representing the mononuclearity of the detergent particles. The mononuclear detergent particles referred to herein have a particle growth degree of 1.5 or less, preferably 1.4 or less, more preferably 1.3 or less. The lower limit is not particularly limited but is preferably 1.0 or more.
Particle growth degree = [average particle diameter of detergent particles obtained by step (C)] / [average particle diameter of base granules]

Such mononuclear detergent particles have the advantage that the particle size distribution is sharp without the formation of particles outside the desired particle size range (aggregated particles) because aggregation between particles is suppressed.

The detergent particle group produced according to the present invention preferably has the following physical properties. In the present invention, the physical properties of the detergent particle group are measured using the particle group that has passed through a sieve having an opening of 1180 μm (excluding the yield). The measurement of yield, fluidity, and bulk density is performed between 10 and 20 minutes after the production of the particles. The average particle size, caking resistance (passage rate), and stain resistance of nonionic surfactants are evaluated using samples stored at 20 to 30 ° C. for 1 to 3 days in a sealed container. To do.

The yield of the soot detergent particle group is calculated by dividing the mass of the sample that has passed through the sieve having an opening of 1180 μm by the mass of the entire sample. The yield is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

The average particle diameter of the soot detergent particle group is preferably 150 μm or more, preferably 500 μm or less, more preferably 150 to 500 μm, still more preferably 180 to 350 μm.

The bulk density of the soot detergent particle group is preferably 300 to 1000 g / L, more preferably 400 to 900 g / L, still more preferably 450 to 850 g / L, and particularly preferably 500 to 800 g / L.

In the present invention, when the bulk density is lowered as desired, for example, a surfactant is added to the spray-dried slurry at 2% by mass or less to lower the bulk density of the base granule. A method of blending a powder raw material having a lower bulk density than the base granule as a powder raw material other than the granule or reducing the amount of the surfactant composition mixed with the base granule can be used.

The fluidity of the detergent particles is preferably 10 seconds or less, more preferably 8 seconds or less, and even more preferably 7 seconds or less as the flow time. The flow time is 100 mL from a hopper for measuring bulk density specified by JIS K3362, that is, a funnel (also called a hopper) shown as an example of an apparent density measuring device in the section of apparent density of JIS K3362: 2008. This is the time required for the detergent particles to flow out.

ケーキ The caking resistance and the stain resistance of the nonionic surfactant are evaluated as follows. Using a filter paper (No. 2 manufactured by ADVANTEC), make a box without a top with a length of 10.2 cm, a width of 6.2 cm, and a height of 4 cm, and fix the four corners with a stapler. In advance, two lines are drawn with an oil marker on the diagonal line of the bottom portion to intersect. A 200 m sample is placed in this box, sealed in an acrylic case, and left in a thermostatic oven at a temperature of 30 ° C. for 7 days to determine caking resistance and non-ionic surfactant stain resistance.

The determination of the caking resistance is performed by determining the passage rate as follows.
<Passing rate>
The sample after being left under the above conditions is gently placed on a wire mesh (or sieve, mesh 5 mm × 5 mm), the mass of the detergent particles that have passed through the wire mesh is measured, and the passage rate for the sample after the test is obtained.
Passing rate (%) = (mass of detergent particles passed (g) / mass of the entire sample (g)) × 100
The passage rate is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more.

Judgment of the nonionic surfactant is performed by visually observing the bleeding of the oily marker drawn on the bottom after the sample is discharged. The evaluation is 1 to 5 ranks, and the status of each rank is as follows.
Rank 1: There is no blur.
Rank 2: Part of the line bleeds and cilia appear. Rank 3: The line bleeds almost entirely, and the average line thickness is less than 2.0 times. Rank 4: The whole line The average line thickness is 2.0 times or more and less than 3.0 times. Rank 5: The entire line is blurred and the average line thickness is 3.0 times or more. In the invention, the evaluation of the degree of bleeding is that of ranks 1 and 2.

洗剤 The detergent particles produced according to the present invention may be a part or all of the particles constituting the powder detergent as the final product. In the case of a part of the particle group constituting the powder detergent as the final product, the detergent particle group produced according to the present invention is a particle group that becomes a powder detergent as the final product by being mixed with other detergent particle groups. Composed. That is, the detergent particle group produced according to the present invention can be used as a powder detergent itself, while it may be used as particles constituting a part of the powder detergent. Therefore, the present invention is also suitable as a method for producing detergent particle groups (in this case, “detergent particle groups” in this specification can be read as “detergent particle groups”).

Other particles mixed with the detergent particles produced according to the present invention mainly include, for example, cleaning aid particles, enzyme particles such as protease, amylase, cellulase and lipase, percarbonate and perborate. Bleach activator particles, TAED, bleach activator particles that react with hydrogen peroxide such as alkanoyloxybenzene sulfonate and alkanoyloxybenzene carboxylic acid to produce organic peracids, alkali metal carbonates and alkali metal silicates Examples include alkali agent particles obtained by granulating an alkali agent. Functional particles may be blended. Examples of the functional particles include softener particles obtained by granulating a softening property clay material such as bentonite, fragrance particles mainly containing a fragrance component, and silicone such as dimethylsiloxane. Antifoaming agent particles containing an antifoaming substance such as Moreover, you may mix with the surfactant particle | grains comprised from the surfactant different from this invention.
Example

The following examples describe the implementation of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.

The present invention will be further described based on the following examples.

The base granules used in Examples 1 to 26 and Comparative Examples 1 to 11 were produced by the following procedure [Step (A)].

Water was added to a 1 m ³ mixing tank having a stirring blade so that the final slurry moisture became 53%, and after the water temperature reached 55 ° C., sodium sulfate, sodium carbonate, and sodium sulfite were added in this order. After stirring for 10 minutes, a 40 mass% sodium polyacrylate aqueous solution was added. Further, after stirring for 10 minutes, sodium chloride and zeolite were added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C. Further, the total mass of this slurry was 1000 kg, and it was blended in the mass ratio of components other than water described in Tables 1 to 3. However, Comparative Example 11 used an acrylic acid-maleic acid copolymer in place of sodium polyacrylate.

This slurry was sprayed at a spray pressure of 25 kg / cm ² from a pressure spray nozzle installed near the top of the spray drying tower. The hot gas supplied to the spray drying tower was supplied at a temperature of 225 ° C. from the bottom of the tower, and was discharged at 105 ° C. from the top of the tower. The moisture in the base granule was as shown in Tables 1-3.

ベース The base granule used in Example 27 was produced by the following procedure [Step (A)].

Water was added to a 1 m ³ mixing tank having a stirring blade so that the final slurry water content was 53%, and after the water temperature reached 55 ° C., sodium sulfate was added. After stirring for 5 minutes, sodium silicate (effective 40%) was added. After stirring for 5 minutes, sodium tripolyphosphate and sodium carbonate were added. After stirring for 15 minutes, 40 mass% sodium polyacrylate aqueous solution was added. Further, after stirring for 10 minutes, sodium chloride was added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 60 ° C. Moreover, the total mass of this slurry was 1000 kg, and it mix | blended with the mass ratio of components other than the water of Table 1.

This slurry was sprayed at a spraying pressure of 35 kg / cm ² from a pressure spray nozzle installed near the top of the spray drying tower. The hot gas supplied to the spray-drying tower was supplied at a temperature of 235 ° C. from the bottom of the tower and discharged at 112 ° C. from the top of the tower. The water content in the base granules was as shown in Table 1.

The physical properties of the obtained base granules are all from 198 μm to 243 μm in average particle size, 480 g / L to 540 g / L in bulk density, 250 gf to 550 gf in particle strength, and 0.33 mL / g to 0.56 mL in pore volume. / G, and the pore diameter was in the range of 0.25 μm to 0.62 μm.

The surfactant compositions used in Examples 1 to 27 and Comparative Examples 1 to 11 were produced by the following procedure [Step (B)].

The surfactant compositions used in Examples 1 to 6 and Comparative Examples 3 to 4 were prepared by mixing a nonionic surfactant and water at a mass ratio shown in Tables 1 and 3 and adjusting the temperature to 60 ° C. I got it.

The surfactant compositions used in Examples 7, 11 to 26 and Comparative Examples 5 to 11 were prepared by using an anionic surfactant (LAS-Na, AS-Na, ES) having an effective content of 50% in a nonionic surfactant. (-Na or α-SFE) aqueous solution and predetermined water were added and mixed so as to have mass ratios described in Tables 1 to 3. The temperature was adjusted to 60 ° C. However, in Example 13 and Comparative Examples 5 to 6, water was adjusted by evaporating water at 60 ° C. after the production. In addition, Example 23 was prepared by neutralizing a fatty acid with 48% caustic soda in a surfactant composition. Furthermore, Example 24 was prepared by adding a predetermined amount of polyethylene glycol. Examples 8 to 10 were obtained by mixing a nonionic surfactant with an anionic surfactant aqueous solution having an effective content of 30% at a mass ratio shown in Table 1 and adjusting the temperature to 60 ° C.

Comparative Example 1 was used separately without mixing the nonionic surfactant and water. Each temperature was adjusted to 60 ° C.

In Comparative Example 2, a nonionic surfactant and an anionic surfactant aqueous solution having an effective content of 50% were used separately without mixing. Each temperature was adjusted to 60 ° C.

Step (C) of Examples 1 to 27 and Comparative Examples 3 to 11 were performed as follows.
100 parts by weight of the base granule group preheated to 50 ° C. was put into a Redige mixer (manufactured by Matsubo Co., Ltd., with a 20 L jacket) and the main shaft (the number of rotations of the main shaft: 80 r / min, the fluid number of the stirring blades: 1.07) ) Started rotating. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotation of the main shaft, the surfactant composition at 60 ° C. is added over 2 minutes so as to be the parts by mass shown in Tables 1 to 3, and then mixed for 6 minutes and then discharged. did. The physical properties of the obtained detergent particles were as shown in Tables 1 to 3.

Step (C) of Comparative Example 1 was performed as follows.
100 parts by weight of the base granule group preheated to 50 ° C. was put into a Redige mixer (manufactured by Matsubo Co., Ltd., with a 20 L jacket) and the main shaft (the number of rotations of the main shaft: 80 r / min, the fluid number of the stirring blades: 1.07) ) Started rotating. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotation of the main shaft, a nonionic surfactant at 60 ° C. is added over 1 minute so as to be the mass part shown in Table 3, and then water at 60 ° C. is added over 1 minute. Then, after mixing for 6 minutes, it was discharged. The physical properties of the resulting detergent particles are as shown in Table 3.

The process (C) of the comparative example 2 was performed as follows.
100 parts by weight of the base granule group preheated to 50 ° C. was put into a Redige mixer (manufactured by Matsubo Co., Ltd., with a 20 L jacket) and the main shaft (the number of rotations of the main shaft: 80 r / min, the fluid number of the stirring blades: 1.07) ) Started rotating. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotation of the main shaft, a nonionic surfactant at 60 ° C. was added over 1 minute so as to have a mass part shown in Table 3, and then an anionic surfactant at 60 ° C. was added 1 It was charged over a period of time, then mixed for 6 minutes and then discharged. The physical properties of the resulting detergent particles are as shown in Table 3.

The components in Tables 1 to 3 are as follows. Also. “*” In the table means that measurement is not possible.
・ Sodium carbonate: manufactured by Central Glass Co., Ltd., trade name: soda ash (light ash)
-Sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., trade name: neutral anhydrous sodium sulfate A0
・ Sodium chloride: manufactured by Naikai Shigyo Co., Ltd., trade name: Nakuru N
-Sodium sulfite: manufactured by Mitsui Chemicals, Inc., trade name: sodium sulfite-sodium silicate: manufactured by Central Glass Co., Ltd., trade name: sodium silicate No. 2-sodium polyacrylate: weight average molecular weight 15,000; GPC Measured by polyethylene glycol conversion, acrylic acid-maleic acid copolymer: sodium salt (70 mol% neutralized), monomer ratio is acrylic acid / maleic acid = 3/7 (molar ratio), weight average molecular weight 70000
・ Zeolite: Zeobuilder, Trade name: Zeobuilder (Zeolite 4A type)
-Sodium tripolyphosphate: manufactured by Shimonoseki Mitsui Chemicals, trade name: sodium tripolyphosphate)
・ Nonionic surfactant 1: An average of 6 moles of ethylene oxide (hereinafter referred to as EO) added to a primary alcohol having 12 to 14 carbon atoms. ・ Nonionic surfactant 2: It has 12 to 14 carbon atoms. Non-ionic surfactant with an average of 21 moles of EO added to a primary alcohol: 9 moles of EO, 2 moles of propylene oxide, and 9 moles of EO on a primary alcohol with 12 to 14 carbon atoms Block addition in order ・ LAS-Na: Alkyl group linear sodium alkylbenzene sulfonate having 12 to 14 carbon atoms ・ AS-Na: Alkyl sulfate sodium salt having 12 to 16 carbon atoms in alkyl group ・ ES-Na: Alkyl Polyoxyethylene alkyl ether sulfate Na salt / α-SFE having 12 to 14 carbon atoms and an average EO addition mole number of 2: Α-sulfo fatty acid methyl ester sodium having 12 to 14 carbon atoms in the kill group Fatty acid sodium: manufactured by Kao Corporation, trade name: Lunac L55 neutralized with 48% caustic soda, polyethylene glycol: manufactured by Kao Corporation , Trade name: K-PEG6000LA (weight average molecular weight; 8500)

Claims

A method for producing detergent particles comprising the following steps (A) to (C):
Step (A): Sodium carbonate, an acrylic acid type polymer in which the proportion of the constituent units of acrylic acid or a salt thereof with respect to all monomer constituent units constituting the polymer is 90 to 100 mol%, and water, A slurry that may contain an insoluble inorganic salt is spray-dried, and contains 25 to 80% by mass of sodium carbonate, 0 to 30% by mass of a water-insoluble inorganic salt, and 2 to 25% by mass of an acrylic acid type polymer, and has surface activity. A step of preparing a base granule having an agent content of 2% by mass or less,
Step (B): a step of preparing a surfactant composition containing a total of 50 to 80% by weight of the surfactant, 15% by weight or more of the nonionic surfactant and 20 to 50% by weight of water,
Step (C): A step of mixing the base granule obtained in the step (A) and the surfactant composition obtained in the step (B) while substantially maintaining the form of the base granule.
The production method according to claim 1, wherein the surfactant composition is used in an amount of 25 to 60 parts by mass with respect to 100 parts by mass of the base granule in the culling step (C).
The surfactant in step (B) comprises a nonionic surfactant and an anionic surfactant, and the mass ratio of nonionic surfactant / anionic surfactant is from 10/1 to 1/3. Item 3. The method according to Item 1 or 2.
The nonionic surfactant is a polyoxyalkylene alkyl ether having an alkyl group having 8 to 22 carbon atoms and an average addition mole number of an oxyalkylene group containing an oxyethylene group of 4 to 25 mol. 4. A method for producing a detergent particle group according to any one of items 1 to 3.
The method for producing a detergent particle group according to any one of claims 1 to 4, wherein the acrylic acid type polymer has a weight average molecular weight of 2,000 to 80,000.
The method for producing a detergent particle group according to any one of claims 1 to 5, wherein the acrylic acid type polymer is polyacrylic acid or a salt thereof.
The method for producing a detergent particle group according to any one of claims 1 to 6, wherein the resulting detergent particle group has an average particle size of 150 to 500 µm.
The method for producing a detergent particle group according to any one of claims 1 to 7, wherein the bulk density of the obtained detergent particle group is 300 to 1000 g / L.
The fluidity of the resulting detergent particle group is 10 seconds or less as the time required for 100 mL of the detergent particle group to flow out from the apparent density measurement funnel defined by JIS K3362. The manufacturing method of the detergent particle group in any one.
A detergent particle group obtained by the production method according to any one of claims 1 to 9.
A method for washing a textile product using the detergent particle group obtained by the production method according to any one of claims 1 to 9.
Use of detergent particles obtained by the production method according to claims 1 to 9 for washing textile products.