WO2000077157A1

WO2000077157A1 - Detergent composition

Info

Publication number: WO2000077157A1
Application number: PCT/JP2000/003792
Authority: WO
Inventors: Hiroyuki Saijo; Hideichi Nitta; Shu Yamaguchi; Hiroyuki Yamashita
Original assignee: Kao Corporation
Priority date: 1999-06-14
Filing date: 2000-06-12
Publication date: 2000-12-21
Also published as: EP1184451A1; EP1184451A4; CN1370225A; CN1193088C

Abstract

A detergent composition which contains 5 to 60 wt % of a phosphate builder and 10 to 60 wt % of a surfactant, has a bulk density of 600 to 1200 g/L and a flowing time of 10 seconds or less, and, with respect to the sum of the products of the weight frequency (Wi) of each particle group obtained by the classification of particles of the detergent by means of a classification apparatus equipped with screens having openings of 2000 νm, 1410 νm, 1000 νm, 710 νm, 500 νm, 355 νm, 250 νm, 180 νm and 125 νm and receiving plates and the proportion of the detergent dissolved (Vi) of each detergent group as measured under the conditions specified in the present specification, satisfies the following formula (1): Σ (Wi - Vi) ≥ 90 (%), and further has a weight frequency of a particle group of 125 νm undersize of 0.10 or less; and a method for producing the detergent composition. The detergent composition is excellent in solubility and dispersibility, and thus can be used for carrying out washing by hand with great ease.

Description

Description Detergent composition Technical field

The present invention relates to a detergent composition and a method for producing the same. Background art

Heavy-duty detergents are used for washing in a washing machine, but may be used for hand-washing when there is a heavy load of stains on fibers. In hand-washing, it has been empirically known that the washing efficiency is good if a heavy detergent solution is applied to the soil and the heavy-duty detergent is sprinkled directly on the part to be washed wet with water and then used. ing. In this case, sufficient lathering is required to improve slippage between the fibers in order to rub the parts to be washed with each other or the other textile parts by hand. In order to facilitate the rubbing operation, a heavy powder detergent having a large amount of water-soluble components is preferable. In addition, when washing with a composition having a large amount of water-soluble components, since the washing liquid in the washing tub is transparent, it is suitable for visually checking whether or not washing has been sufficiently performed as a result of washing. From such a background, a powder heavy detergent containing a large amount of a water-soluble component, that is, a powder heavy detergent containing a large amount of phosphate builder is suitable. Further, in order to shake a desired amount of the heavy powder detergent onto the portion to be washed, it is necessary that the powder has high fluidity.

On the other hand, heavy-duty detergents have been densified to provide significant advantages in improving transport efficiency and simplicity in weighing users. However, the consolidation of detergent particles raised concerns about solubility. Particularly in the case of hand-washing, there is a concern that the detergent particles do not readily dissolve during washing and that the foaming speed, which causes slippage between cloths, is reduced. On the other hand, washing machines are being designed in consideration of consumer demand, water saving and energy saving. For example, in the case of Japanese-made washing machines, large capacity There is a tendency to save water, and a short agitation mode is set, which emphasizes the short-time washing mode and the reduction of clothing damage. These tend to decrease the work load of the washing machine (meaning mechanical power X hours), which greatly reduces the solubility of detergent particles, deteriorating the cleaning power, and leaving residue on clothes. Is a major issue. In addition, in European and American washing machines, it is important to lower the washing temperature from the viewpoint of energy saving during washing, and a detergent with good solubility is required.

As described above, in order to improve the efficiency of not only washing using a washing machine made in each country but also washing by hand washing, the powder has high fluidity, foams quickly, is easy to wash, and the agglomeration of detergent particles disappears. There is a need for a detergent with a high dissolution rate that contains a phosphate builder that is fast.

However, the solubility of detergents containing phosphate builder to date has been insufficient. If the solubility of the detergent particles is simply improved, the fluidity of the powder is reduced, or the dispersibility in water is reduced, so that the detergent powder acts on wet clothes during hand washing at low temperatures. At the time of washing or washing at a low water temperature in a washing machine, agglomerates of detergent particles tend to be formed, which did not sufficiently satisfy all the above requirements. Disclosure of the invention

An object of the present invention is to provide a detergent composition containing a phosphate builder which has excellent detergency even when the work load of a washing machine is low, and has excellent particle solubility and dispersibility so that it is easy to wash by hand. is there.

These and other objects of the invention will be apparent from the description below.

That is, the gist of the present invention is:

It contains 5 to 60% by weight of a phosphate builder and 10 to 60% by weight of a surfactant, has a bulk density of 600 to 1200 g ZL, and a flow time of 10 seconds or less. Detergent composition Sieves and pans with openings of 2000 m〃, 1400 Aim, 100 m 0m, 710 m, 500 m, 355 tm, 250 m, 180 mimm and 125 m The weight frequency W i of each classified particle group obtained by classifying the detergent particles by using a classifier consisting of: and the dissolution rate V i of each classified particle group measured under the following measurement conditions. A detergent composition in which the sum of the products satisfies the following formula (1), and the weight frequency of the classified particles having a particle size of less than 125 / m is 0.10 or less:

∑ (WiVi) ≥ 90 (%) (1)

[Measurement conditions: 1.000 g ± 0.01 0 g of a sample is poured into 1.00 L ± 0.03 L of water at a hardness of 4 ° 0 ^ [at 5 ° C ± 0.5, and a 1 L beaker ( After stirring with a cylindrical stirrer (length: 35 mm, diameter: 8 mm) at a rotation speed of 800 rpm in an inner diameter of 105 mm), melt it with a standard sieve specified by JISZ 8801 (opening: 74 zm). The residue is filtered. The dissolution rate Vi of the classified particles is calculated by the following equation (2). Here, i means each classified particle group.

V i = (1 -T i / S i) X 100 (%) (2)

(Here, S i represents the input weight (g) of each classified particle group, and T i represents the dry weight (g) of the dissolved residue of each classified particle group remaining on the screen after filtration.) And its manufacturing method

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 (1) and (2) are diagrams showing the steps of a classification operation in the production method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

[1] Composition

The content of the phosphate builder in the present invention is from 5 to 60% by weight, preferably from 10 to 50% by weight of the detergent composition, from the viewpoint of the slipperiness of the laundry to be washed during hand washing. %, More preferably 15 to 45% by weight.

As the phosphate builder, one or more selected from tripolyphosphate, orthophosphate, pyrophosphate and the like are preferable. The content of triphosphate in the total phosphate builder is 80 to 97% by weight, the content of orthophosphate is 1 to 10% by weight, and the content of pyrophosphate is 2 to 10% by weight. Suitable (content calculated as anhydride). As the counter ion, an alkali metal ion is preferable, and particularly, a sodium ion and a potassium ion are preferable. The content of sodium ions and potassium ions in all the counter ions is preferably at least 70% by weight, more preferably at least 85% by weight.

The surfactant content in the present invention is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, and still more preferably from the viewpoint of obtaining detergency and desired powder properties. Or 27-45% by weight. The surfactant contains an anionic surfactant and / or a non-ionic surfactant, and may contain a cationic surfactant and an amphoteric surfactant as necessary.

As anionic surfactants, alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, hypoolefin sulfonate, hysulfo fatty acid salt or ester thereof, alkyl or alkenyl ether carboxylate And fatty acid salts. The content of the anionic surfactant is preferably 1 to 50% by weight, more preferably 5 to 30% by weight of the detergent composition in terms of detergency.

As the counter ion, an alkali metal ion is preferable in terms of improving the detergency. Particularly, from the viewpoint of improving the dissolution rate, potassium ions are preferable, and the content of potassium ion in all the counter ions is preferably 5% by weight or more, more preferably 20% by weight or more, and particularly preferably 40% by weight or more.

As nonionic surfactants, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene fatty acid esters And polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene alkylamines, glycerin fatty acid esters, higher fatty acid alcohol amides, alkyl glycosides, alkyl glucose amides, and alkylamine oxides. In terms of detergency, an adduct of ethylene oxide with an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, or a mixed adduct of ethylene oxide and propylene oxide, wherein the average alkylene oxide is A polyoxyalkylene alkyl ether having an addition mole number of 5 to 30, preferably 6 to 15 is preferredo

Further, in terms of detergency and solubility, polyoxyethylene polyoxypropylene polyoxyethylene alkyl ether is preferred. The compound can be obtained by reacting an ethylene oxide adduct of an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, with propylene oxide and further ethylene oxide. Further, among the above polyoxyethylene alkyl ethers, those having a narrow distribution of the alkylene oxide chain length are preferred.

The content of the nonionic surfactant is preferably 1 to 50% by weight, more preferably 5 to 30% by weight of the detergent composition from the viewpoint of detergency.

Examples of the cationic surfactant include alkyltrimethylammonium salts and the like, and examples of the amphoteric surfactant include carbobetaine-type and sulfobetaine-type surfactants. The content of each of the positive surfactant and the amphoteric surfactant is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight of the detergent composition.

The detergent composition of the present invention may contain water-soluble inorganic salts such as carbonates, bicarbonates, silicates, sulfates, sulfites, and phosphates. As the counter ion, an alkali metal ion such as a sodium ion and a potassium ion is particularly preferable. Here, from the viewpoint of low-temperature dispersibility after standing in cold water for a long time, the salts, especially carbonates, are preferably 40% by weight or less, more preferably 5 to 3% by weight of the detergent composition in terms of anhydride. 0% by weight, more preferably 5 to 25% by weight. The detergent composition of the present invention may contain a crystalline silicate. From the viewpoint of sequestering ability / moisture absorption resistance, the Si 0 ₂ ZM ₂₀ molar ratio (M is an alkali metal atom) is preferably 0.5 or more, and preferably 2.6 or less from the viewpoint of alkali ability. 5 to 2.2 are particularly suitable. The crystalline silicate preferably has an average particle size of about 1 to 40 m from the viewpoint of high-speed dissolution and powder physical properties.The content of the crystalline silicate is 0. It is preferably from 5 to 40% by weight, more preferably from 1 to 25% by weight. In particular, a combination with sodium carbonate is preferred.

In addition, the detergent composition of the present invention is preferably blended with a cation exchange polymer having a carboxylic acid group and a Z or sulfonic acid group in terms of sequestering ability and dispersing ability of solid particle stains. In particular, salts of acrylic acid-maleic acid copolymers having a molecular weight of 1,000 to 100,000, polyacrylates and molecular weights described in JP-A No. 54-52196 of 8 to 1 million, preferably 5,000 to 200,000 polyacetate carboxylate such as polyglyoxylic acid is blended. The cation exchange polymer is preferably contained in an amount of 0.5 to 12% by weight, more preferably 1 to 7% by weight, particularly preferably 2 to 5% by weight of the detergent composition from the viewpoint of detergency.

The detergent composition of the present invention may contain a crystalline aminosilicate such as A-type, X-type, or P-type zeolite. The average primary particle diameter is preferably from 0.1 to 1. The content of the crystalline aluminosilicate is preferably 3 to 15% by weight of the detergent composition. Preferred as the crystalline aluminosilicate is A-type zeolite (for example, trade name "Toyovirda-1": manufactured by Tosoichi Co., Ltd.), which is also preferable in terms of sequestering ability and economy. Here, the value of the oil absorption capacity of the A-type zeolite according to the JISK 5101 method is preferably at least 4 OmL / 100 g. In addition, P type (for example, trade name “Doucil A24J,“ ZSE064 ”, etc.); all manufactured by Crosfie 1d; oil absorption capacity 60 to 15 OmLZl 00 g), X type (for example, trade name“ We ssa 1 It hXDj.; manufactured by Degu ssa; oil absorption capacity 8 O l O OmLZl OO g), and suitable zeolite described in WO9842622 is also suitable crystallinity. Examples include aluminosilicates.

For the purpose of preventing seepage of liquid components such as nonionic surfactants, an amorphous aluminosilicate having an oil absorption capacity of at least 8 OmL / 100 g according to the JISK 5101 method can be blended. As the amorphous aluminosilicate, to maintain the long-term high solubility even after the storage (not degraded) in _{_{view, S i 0 2 A 1 2}} 0 3 ( molar ratio) is 4.0 or less, Preferably, it is 3.3 or less, and JP-A-5-501 publication, column 4, line 34 to column 6, line 16 (especially column 4, line 43 to 49) (Oil-absorbing carrier) ゃ Japanese Patent Application Laid-Open No. 6_1798999, column 12, line 12, line 13 to column 17, line 17, column 17, line 34 to column 19, line 17 Among them, those having the properties described are listed, and among them, the volume of pores with a pore diameter of 0.015 to 0.0 measured with a mercury porosimeter (manufactured by Shimadzu Corporation, "SH IMADZU Pore Sizer 9320J") is 0. It is preferable that the volume of 0.5 to 2 zm and the volume of 0.5 to 2 zm is 0.3 OmLZg or more The content of the amorphous aluminosilicate is 0.1 to 20% by weight of the detergent composition. The crystalline a, which is a water-insoluble inorganic salt in the present invention, is preferred The total amount of the minosilicate, the amorphous aluminosilicate and the crystalline silicate having a low dissolution rate in water is preferably less than 25% by weight of the detergent composition in view of the ease of hand washing and washing. It is preferably less than 20% by weight, more preferably less than 15% by weight, and less than 200% by weight, preferably less than 100% by weight with respect to phosphate builder. Desirably.

The detergent composition of the present invention includes organic acid salts such as citrate and ethylenediaminetetraacetate; dispersants or color transfer inhibitors such as carboxymethylcellulose, polyethylene glycol, polyvinylpyrrolidone and polyvinyl alcohol; Bleaching agents such as salts, compounds described in JP-A-6-31670 and bleaching activators such as tetraacetylethylenediamine, enzymes such as proteases, cellulases, amylases and lipases; A stilbene-type fluorescent dye, an antifoaming agent, an antioxidant, a bluing agent, a fragrance, and the like can be appropriately compounded. [2] Bulk density

The bulk density of the detergent composition measured by JISK 3362 is 600 to 1200 gZL, and from the viewpoint of improving transport efficiency and user convenience, is 600 g / L or more, preferably 6 g / L or more. 5 O gZL or more, more preferably 70 O gZL or more, and 1200 gZL or less, preferably 1 g, from the viewpoints of securing voids between particles and improving dispersibility by suppressing the increase in the number of contact points between particles. It is at most 5,000 gZL, more preferably at most 850 g / L.

[3] Particle size

The detergent composition of the present invention is excellent in solubility per detergent particle and prevention of aggregation between detergent particles. Here, agglomeration between detergent particles means that under the conditions of low mechanical force and cold water, a surfactant capable of forming liquid crystals and a part of inorganic salts that form hydrated crystals such as carbonates and sulfates are dissolved. This is a phenomenon in which high-viscosity liquid crystals are formed between the detergent particles or recrystallized into hydrates earlier than the remainder is dissolved after the start. Therefore, in the particle size of the detergent composition of the present invention, the weight frequency of the classified particles having a particle size of less than 125 / m is 0.10 or less from the viewpoint of preventing aggregation between the detergent particles.

From the viewpoint of improving low-temperature dispersibility and fluidity, it is preferable that the content of fine particles in the detergent composition is small. The weight frequency of the classified particles having a particle diameter of less than 125 / m is 0.10 or less, preferably 0.08 or less, more preferably 0.06 or less, and particularly preferably 0.04 or less. The weight frequency of the classified particles having a particle diameter of 125/111 or more and less than 180 / m is preferably 0.20 or less, more preferably 0.10 or less, and particularly preferably 0.05. It is as follows. Here, with respect to the fine particles, it is preferable that each weight frequency has a relationship of [classified particle group having a particle size of less than 125 m] ≤ [classified particle group having a particle size of from 125 m to less than 180 m].

In addition, the content of coarse particles in the detergent composition is small in view of the high-speed solubility per particle. Preferably not. That is, the weight frequency of the classified particle group having a particle diameter of 1000 / zm or more is preferably not more than 0.03, more preferably not more than 0.01, and particularly preferably substantially not included. The weight frequency of the classified particle group having a particle diameter of 7100 m or more and less than 1000 zm is preferably 0.10 or less, more preferably 0.05 or less, and particularly preferably 0.03 or less. The weight frequency of the classified particle group having a particle diameter of 500 / m or more and less than 710 m is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0.03 or less. . Here, for the coarse particles, each weight frequency is [classified particle group with a particle size of 100 m or more] ≤ [particle size with a particle size of 7100 // m or more and less than 100 am] ≤ [particle Classified particle group having a diameter of 500 m or more and less than 7 10 m] is preferable. The average particle diameter of the detergent composition of the present invention is preferably 150 to 500 m, more preferably 20 to 50 m. 0 to 400 m, particularly preferably 250 to 350 m. Here, the average particle diameter (Dp) is a diameter of 50% by weight, and can be measured using the above classifier. That is, after the classification operation, the weight frequency is accumulated in order from fine particles to coarse particles, the opening of the first sieve at which the cumulative frequency becomes 50% or more is am, and is larger than a 段. When the mesh size of the sieve is b / m and the integration of the weight frequency from the saucer to the sieve of a is c%, and the weight frequency on the sieve of azm is d%, the following formula (3) is used. You can ask.

Dp = 1 0 ^A (3)

However,

d

5 0-(C x 1 o g b)

l og D— 1 o g a

d

l og b-1 oga [4] Solubility of classified particles

In measuring the solubility of each classified particle group, first, for example, a sample 1.0000 g ± 0.010 g precisely weighed using “Electronic balance ER-180A type” manufactured by Kensei Kogyo Co., Ltd. Into a 1.0 L soil and 0.03 L water at 5 ° C ± 0.5 ° C with a hardness of 4 ° DH so as not to cause agglomeration between the particles. After stirring with a cylindrical stirrer (length: 35 mm, diameter: 8 mm) at a rotation speed of 800 rpm in an inner diameter of 105 mm), a standard sieve (JISZ8801 standard) was used. Filter (mesh size: 74 m) (Use a sieve having a sieve area of 35 cm ² or more and a weight of 10 g or less, and measure the weight in advance.) Subsequently, the residue of each classified particle group remaining on the sieve was dried together with the sieve in an electric dryer at 105 ° C for 1 hour, and desiccated with silica gel with enhanced activity. Allow to cool for 30 minutes at (25 ° C), then weigh. By subtracting the weight of the sieve from this weight, the dry weight of the residue of each classified particle group can be derived. Specific measurement conditions are the same as the dissolution measurement conditions described above. Under these conditions, the powder detergent composition having a dissolution rate of 90% or more was found to be very easy to dissolve and lose particles even at the time of manual washing at room temperature or lower, and to have a high foaming rate. Was.

[5] Solubility of detergent composition

The solubility of the detergent composition of the present invention is represented by the sum of the products of the weight frequency W i of each classified particle group and the solubility V i of each classified particle group (that is, ∑ (Wi · Vi)). . The solubility of the detergent composition of the present invention is 90% or more, preferably 94% or more, more preferably 97% or more. The dissolution rate Vi of the classified particles is calculated by the following equation (2). Here, i means each classified particle group.

V i = (1— T iZS i) X 1 0 0 (%) (2)

(Here, Si indicates the input weight (g :) of each classified particle group, and Ti indicates the dry weight (g) of the residue of each classified particle group remaining on the screen after filtration.) INDUSTRIAL APPLICABILITY The detergent composition of the present invention is easy to sprinkle a desired amount on an object to be washed in hand-washing, has a fast dissolution of particles, has an excellent foaming rate, and has a phosphate builder as a main builder. Can be done efficiently. In addition, in irrigation using a washing machine, since it has extremely high solubility even in cold water conditions, it not only has the effect of eluting the washing components into the washing bath more quickly to improve the washing power, but also has an extremely low Even under laundry conditions, the probability of remaining undissolved is extremely low.

[6] Hand wash solubility of detergent composition

The detergent composition of the present invention also shows remarkably excellent hand-washing solubility as compared with conventional detergent compositions. The hand-washing solubility is a measure of the solubility when the detergent composition is previously dissolved in a container such as a basin before hand washing of contaminated clothing, and is indicated by a dissolution time. Hand washing is a common washing habit for pre-washing contaminated clothing, etc., not only for users who mainly use hand washing but also for those who mainly use a washing machine. Is important as a measure of greater convenience.

A specific measuring method is a polypropylene basin with a maximum opening diameter of 31 cm, a bottom part of 24 cm, and a height of 13 cm (for example, KW-30 type washing tub manufactured by YA ZAKI, content volume 8.2 L) ), Add 5.0 L of tap water at 25 ° C. Then, spray 15 g of the detergent composition to be tested uniformly and quickly (within 3 seconds as a guide) over the entire surface of the water so that it does not solidify in one place. From that point, a skilled panelist spreads five fingers with one hand (dominant arm) and gently strokes the bottom of the basin with his fingertip while sensing detergent particles present at the bottom of the basin with his fingertip (ventral side of the finger) Start the stirring). Here, stirring is performed in such a manner that clockwise rotation and counterclockwise rotation are alternately repeated in five rotation cycles, and stirring is performed so that the sample solution does not spill out from the basin wall. The rest is about 1.0 second as a guide). In this way, stirring is continued until detergent particles are no longer detected, and the time is measured. Panelists continued on test samples The test is repeated until the deviation of the measurement time of the three measurements is within 5% of the soil, and the average time of the three measurements is taken as the hand-washing dissolution time of the panel.

The panelists will be conducted by 10 or more persons. The average value of the panelists' hand-washing dissolution times in the middle 60% excluding the top 20% and bottom 20% panelists shall be used as the hand-washing dissolution time of the tested detergent composition.

Hand washing solubility of the detergent composition of the present invention is preferably 80 seconds or less, more preferably 60 seconds or less, further preferably 50 seconds or less, and particularly preferably 40 seconds or less.

[7] Liquidity

When the detergent composition of the present invention is hand-washed, a desired amount of detergent is easily sprinkled on a portion to be washed, and when the detergent composition is put into a washing machine, when the composition concentrates locally, it disperses when exposed to water. In order to reduce the decrease, it is preferable that the fluidity is excellent (it is easy to sprinkle evenly). The flow time (the time required for the powder of 10 OmL to flow out of the hopper for bulk density measurement specified by JISK 3362) is 10 seconds or less, preferably 8 seconds or less, more preferably Is less than 6.5 seconds.

[8] Manufacturing method

The detergent composition of the present invention comprises an unclassified detergent particle group containing 5 to 60% by weight of a phosphate builder and 10 to 60% by weight of a surfactant (hereinafter, also referred to as a base detergent particle group. In addition, the base detergent particle group includes a classification particle group obtained by performing a classification operation and a particle size adjustment operation a plurality of times.) The production process can be performed by performing a classification operation and a particle size adjustment operation.

(Process 1) Manufacturing process of base detergent particles

One form of the method for producing the base detergent particles is a jet of surfactant or builder. A method of obtaining atomized particles and increasing the density of the particles can be used. As this method, for example, a method of increasing the bulk density by stirring and granulating the spray-dried particles with a vertical or horizontal mixer can be mentioned. Examples thereof include a method of agitating and granulating spray-dried particles described in Japanese Patent Application Laid-Open No. 2-49100, and a method of molding the dried particles described in Japanese Patent Application Laid-Open No. Sho 62-169900. Crushing and granulation after crushing,

A method of kneading and mixing the detergent raw materials described in JP-A No. 7 (Kokai) No. 7 to crush the solid detergent obtained, and a method of dispersing an anionic surfactant in a high-speed mixer described in JP-A-3-31399. A method in which the acid precursor is dry-neutralized with a granular solid refining agent and then granulated by adding a liquid binder can be used.

Another embodiment of the method for producing the base detergent particles is described in Japanese Patent Application Laid-Open No. H10-17662.

The mixture of the acid precursor of the nonionic surfactant and the anionic surfactant capable of lamellar orientation described in Japanese Patent Publication No. 0 is tumbled by a stirring granulator at a temperature not lower than the neutralizable temperature. For example, a method of granulating while performing the method can be used.

(Process 2) Classification and particle size adjustment process

The detergent composition of the present invention can be obtained by classifying and adjusting the particle size of the base detergent particles. Examples of the classification method include a method using a circular / rectangular vibrating sieve, an ultrasonic vibrating sieve having an ultrasonic vibrator attached thereto, a wind classifier / centrifugal classifier, and the like. After performing at least one-stage classification operation on the base detergent particles, the weight frequency of each of the classified particles on the sieve and the classified particles below the sieve is measured with respect to the input amount of the base detergent particles. It can be obtained by blending the classified particle groups so that the above formula (1) is satisfied and the weight frequency of the classified particle groups of less than 125 m is 0.10 or less.

The classification operation may be a single-stage operation described in Fig. 1 (1), or may be a two-stage or more operation described in Fig. 1 (2) as necessary. For example, coarse particles are separated by the first-stage classification from the viewpoint of high-speed solubility per particle, and the second-stage classification is performed from the viewpoint of low-temperature dispersibility. In the operation, fine particles, for example, classified particles having a particle size of less than 125 zm are separated, and a part or all of the fine particles are subjected to a granulating operation, and then subjected to the base detergent particles again to obtain a desired detergent composition. be able to. As a blending method, a batch-type or continuous-type blending method such as a V-type mixer can be used.

In addition, after excessive granules of the base detergent particles not used for particle size adjustment among the base detergent particles are granulated and Z or crushed, the detergent composition is used again as a base detergent particle group, so that the detergent composition can be produced in high yield. Obtainable. That is, as in the case of fine particles having a particle size of less than 125; zm, particles having good solubility per particle, but a particle group in which the dispersibility of the detergent composition is likely to decrease due to an increase in the number of indirect particles, are granulated. After performing the particle size increasing treatment such as operation, it can be reused as a base detergent particle group. In the detergent composition of the present invention, it is particularly important to reduce the weight frequency of the classified particles having a particle size of less than 125 zm, and this operation makes the production economical. On the other hand, surplus coarse particles having poor solubility per particle can be reused as a base detergent particle group after subjecting to means for reducing the particle size such as crushing operation.

That is, the classified particles not used in the above steps 1 and 2 are subjected to a granulation operation based on the dissolution rate Vi, for example, granules having a Vi of 90% or more, and a Vi of less than 90%. The coarse particles are preferably subjected to a crushing operation or the like to be reused as a base detergent particle group. Hereinafter, a fine granulation operation and a coarse particle disintegration operation will be exemplified.

(Fine granulation operation)

Excess fine particles may be recovered by adding the fine particles as they are to the manufacturing process of the base detergent particles in step 1. In addition, as another collection method, for example, a method of compacting and granulating in a vertical / horizontal stirring granulator, an extrusion method using an extrusion granulator, a compression molding method such as pre-ketting, etc. good. Also, a binder can be added during molding.

(Coarse particle crushing process) Excess coarse particles can be reused as a base detergent particle group by reducing the particle size, for example, by crushing. Examples of coarse particle crushers include impact crushers such as a hammer crusher, impact crushers such as an atomizer and a pin mill, and shear crushers such as a flash mill. These may be a single-stage operation or a multi-stage operation of the same or different types of pulverizers. It is preferable to add fine powder as an in-machine adhesion inhibitor or a pulverized surface modifying agent. The fine powder is preferably an inorganic powder such as triboriphosphate, aluminosilicate, silicon dioxide, bentonite, talc, clay amorphous silica derivative, and more preferably a crystalline or amorphous aluminosilicate. Fine powders of inorganic salts such as soda ash and sodium sulfate are also used.

In addition, a surface modification step may be provided for the purpose of fixing and smoothing the surface modifier in order to improve the fluidity of the crushed particles. For example, the composition is fed batchwise or continuously into a rotary cylinder machine or a stirrer to perform rolling or stirring.

By the combination of the fine granulation operation and the coarse particle disintegration operation, a detergent composition can be economically obtained in a high yield from the surplus classified particles in the step 2. In addition, enzymes, pigments, fragrances, and the like can be blended after the classification and particle size adjustment steps. Example

Evaluation 1 (Solubility of detergent composition)

A washing net (model number: AXW22A-5RU0, mesh size: 300 x 640 zm) was attached to the side of the irrigation tank of the washing machine manufactured by Matsushita Electric Industrial Co., Ltd. “Aizumago NA-F70VP1J. 3 kg (50% by weight of cotton underwear, 50% by weight of polyester Z cotton blended Y-shirt), 44.0 g of the detergent composition of the example was evenly sprayed and poured, and tap water at 5 ° C was poured. After washing (excluding the rinsing step), the amount of the detergent composition remaining in the washing net was visually judged according to the following evaluation criteria. A water temperature of 5 ° C is a disadvantageous condition for the solubility of the particles in a washing time of 3 minutes, and the evaluation criteria A, B and C indicate that the detergent composition has excellent solubility. And

〔Evaluation criteria〕

A: Residual detergent particles are almost zero (standard of remaining detergent particles: 0 to 5). B: No residual detergent particles (approximately 6 to 15 residual detergent particles).

C: Detergent particles hardly remain (approximately 16 to 30 residual detergent particles). D: A small amount of detergent particles remains (30 to 100 particles of remaining detergent particles).

E: Detergent particles are left in large quantities (approximately 10 1 or more residual detergent particles, and some residue is not found). Evaluation 2 (Dispersibility of detergent composition)

25.0 g of the detergent composition of the example was collected near one outer circumference of the six-part fan-shaped depression of the pulse of Matsushita Electric Industrial washing machine `` Aizumago NA-F42Y1 '' Put 1.5 kg of clothing (same as evaluation 1) into the washing tub without breaking it, and keep the detergent composition at 5 ° C at a flow rate of 10 minutes to prevent direct contact with water. 22 L of water was injected, and the mixture was allowed to stand still after the injection. After 3 minutes from the start of water injection, stirring was started in a weak water flow (hand washing mode), and after stirring for 3 minutes, drained, and the state of the detergent composition remaining in clothing and irrigation tanks was visually judged according to the following evaluation criteria. . In addition, the stirring power in this evaluation is extremely weaker than the standard, and the evaluation criteria I and II indicate that the detergent composition has excellent dispersibility. The “aggregate” described below refers to a lump having a diameter of 3 mm or more in which the detergent particles are aggregated.

〔Evaluation criteria〕

I: There is no aggregate.

I I: Almost no aggregate (1 to 5 lumps with a diameter of about 3 mm are found).

Π 少量: A small amount of aggregate remains (lumps with a diameter of about 6 mm are found, and less than 10 lumps with a diameter of 3 to 1 Omm are found). IV: A large amount of aggregate remains (many lumps exceeding 6 mm in diameter are observed)

Evaluation 3 (Hand wash solubility)

The hand wash solubility was measured according to the measurement method described in the above “[6] Hand wash solubility of detergent composition”. The washbasin was a KW-30 type washing tub manufactured by YAZAK I, and the panel was implemented by 10 people.

Production Example 1 (hereinafter, parts by weight are referred to as "parts")

Straight chain alkyl (10 to 13 carbon atoms) 100 parts of a 25% by weight aqueous solution of sodium benzenesulfonate 100 parts, alkyl (12 to 16 carbon atoms) 3 parts of sodium sulfate, polyoxyethylene (average number of moles of EO added 8) alkyl (C12-14) Ether (hereinafter referred to as "nonionic surfactant") 2 parts, Stone (C14-20) 3 parts, Sodium tripolyphosphate 30 parts, No.1 sodium silicate 2 parts, Carbonic acid Sodium 10 parts, potassium carbonate 2 parts, sodium sulfate 2 parts, sodium sulfite 0.5 parts, sodium polyacrylate (average molecular weight 10,000) and acrylic acid maleic acid copolymer (“Sokalan CP5”)

10 parts of a 40% by weight aqueous solution containing 1/3 (weight ratio), 1.5 parts of polyethylene glycol (average molecular weight 8.500), 1.5 parts of a fluorescent dye (0.1 part of "Tinopearl CBS-X",

"Whytex SA" (0.1 part) was mixed with 49.5 parts of water to prepare a slurry having a solid content of 40% by weight (temperature: ⁶⁵ eC). Particles having a bulk density of about 300 gZL were obtained using a countercurrent spray dryer. Volatile content (105, 2 hour weight loss) was 2.1 mass. Next, 87 parts of the particles and 0.5 part of 4A zeolite (average particle size of about 3 μm) were put into a high-speed mixer (internal volume: 25 L, manufactured by Fukae Kogyo) and mixed. Next, 5 parts of crystalline silicate powder (crushed product of SKS-6, average particle size of 27 μm) was added, and the mixture was further crushed and granulated with stirring by adding 4 parts of the above nonionic surfactant by spraying. At that time, add 3.5 parts of the above zeolite powder just before the end. Then, the surface was coated to obtain a base detergent particle group. The total charge was 5 kg. Production Example 2

Linear alkyl (10 to 13 carbon atoms) 56 parts by weight of a 25% by weight aqueous solution of potassium benzenesulfonate, —sulfo fatty acid (14 to 16 carbon atoms) sodium methyl ester 8 parts, same nonionic surface activity as in Production Example 1 1 part, 7 parts of the same stone as in Production Example 1, 20 parts of sodium tripolyphosphate, 1 part of No. 1 sodium silicate, 5 parts of sodium carbonate, 16 parts of potassium carbonate, 1.1 parts of sodium sulfate and 1.5 parts of sodium sulfite 5 parts of a 40% by weight aqueous solution of sodium polyacrylate (average molecular weight 10,000), 2 parts of the same polyethylene glycol as in Production Example 1, 0.2 parts of a fluorescent dye (“Tinopearl CBS-X” 0.2 parts, “WHITEX SA ”(0.1 part) was mixed with 45.9 parts of water to prepare a slurry having a solid content of 48% by weight (temperature of 65 ° C). Using a counter-current spray dryer, particles having a bulk density of about 32 O gZL were obtained. The volatile content (105 ° C., loss for 2 hours) was 5% by weight. Next, the above particles 50 kg / H, sodium carbonate (heavy ash) 4 kgZH, the same crystalline silicate powder 1 kgZH as in Production Example 1, and the same nonionic surfactant 3 kg ZH as in Production Example 1 It was continuously added to Ni-da-1 (made by Kurimoto Iron Works). At the outlet of the kneader, a twin-screw extruder (“Pellet Double”: made by Fuji Baudal) was installed to obtain a cylindrical pellet with a diameter of about 3 mm. To this 100 parts of pellets, 5 parts of powdered zeolite (average particle size of about 3 zm) was added as a disintegration aid, and a 1.5 mm screen was opened while passing cool air at 14 ° C. The mixture was pulverized and granulated with a FIMILL (manufactured by Hosokawa Micron) equipped with a base, to obtain a base detergent particle group. Production Example 3

Redige mixer “FKM-13D” (Matsubo Co., Ltd.) Using a high-speed mixer, 32% by weight of linear alkyl benzene sulfonic acid (LAS: molecular weight 322), sodium tripolyphosphate (STPP: average particle size 1) 1.2〃m) 20% by weight, Zeolite 12% by weight, sodium carbonate 29.9% by weight, Glauber's salt 1.6% by weight, acrylic acid maleic acid copolymer ("Sokalan CP5 J") 0.5% by weight, fluorescent dye ("Tinopearl CBS—XJ 0.2 Weight%, "WHITEX SA" 0.1 weight%), enzyme (Novo Nordisk, "Sapinase 18T type WJ") 0.5 weight%, fragrance 0.2 weight%, moisture 3.0 weight% The base detergent particles (1) were produced in units of 35 kg This mixer was equipped with a stirring blade and a shearing machine equivalent to a chopper for disintegrating and disintegrating.

Powder mixing>

7.0 parts of sodium tripolyphosphate, which is a solid component, sodium carbonate (“light ash”, manufactured by Central Glass Co., Ltd., average particle size 56.1 τη) 12.61 parts, and fluorescent dye 0.1 1 part was processed by a Lodige mixer under the conditions of a stirring blade rotation speed of 130 rpm (peripheral speed of 3.4 m / s) and a shearing machine rotation speed of 285 0 rpm (peripheral speed of 27 m / s). Mix for minutes.

Water (0.20 parts) was added as a reaction initiator into the mixer and mixed under the same conditions for 1.5 minutes.

While operating the mixer under the same conditions as above, premixed straight-chain alkyl (10 to 13 carbon atoms) sodium benzenesulfonate (LAS) 10.92 parts and 98% sulfuric acid 0.23 Parts were added in 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. At this stage, the temperature reached a maximum of 75 ° C. The reaction mixture was granular throughout this stage. The above LAS is S0 ₃ gas It was produced by a sulfonation method and contained 0.16 parts of sulfuric acid. Sodium carbonate was about six times the amount needed to neutralize LAS and sulfuric acid. After the addition of LAS, the mixer was continuously operated under the same conditions for 1 minute to complete the neutralization reaction and the granulation operation.

At the completion of the neutralization reaction and the granulation operation, while operating the mixer under the same conditions as described above, 40% by weight of acrylic acid-maleic acid copolymer (0.18 parts of an effective component) 0.45 parts by weight of an aqueous solution Was added to the mixer and mixed for 1.5 minutes. Then, 4.2 parts of powdered zeolite (average particle size: about 3 m) was added as a surface modifier, and the surface was coated by operating the mixer for another 2 minutes. Thereafter, 0.175 parts by weight of the enzyme and 0.07 parts by weight of the fragrance were added to obtain a base detergent particle group (1).

(Classification operation of base detergent particles)

The classification operation was performed on each of the base detergent particle groups in Production Examples 1 to 3 using the above-described classification device. Specifically, 100 times of the sample was put from the top of the 2000 m sieve at the top of the classifier, and the lid was put on it. A tapping machine (made by HE IKO SE I SAKUSHO, tapping: 156 times Z Min., Rolling: 290 times), and after shaking for 10 min., Recover the sample remaining on each sieve and saucer for each sieve, and the required amount of more than 1410 tm to 2000 m Less than 1, 000 m to less than 1400 m, less than 700 tzm to less than 100 m, less than 500 m / m to less than 700 m, more than 350 m to 350 m 0 m or less, 250 cm or more to less than 355 m, 180 tzm or more to less than 250 am, 125 zm or more to less than 180 m / m, dish to 125 zm (less than 125 cm) A sample of each classified particle group was obtained.

(Classification operation of enzyme particle group) The same classifying operation as for the base detergent particle group was performed on the enzyme particle group A (manufactured by Novo Nordisk, "Sapinase 18T Type W") to obtain each classified enzyme particle group.

[Measurement of dissolution rate V i of each classified particle group]

According to the above-described measurement method, the dissolution rate of each classified particle group was measured. The results are shown in Table II. Table 1 Enzyme A

59.4

74.4

81.3

95.0

99.7

Example 1

Using the base detergent particles obtained in Production Examples 1 to 3 and the classified particles of the enzyme particles A, the particle size was adjusted according to the following method, whereby the high bulk density detergent compositions of Examples 1 to 9 were obtained. Table 2 shows the average particle size, bulk density, fluidity, and ∑ (Wi · Vi) of the obtained detergent composition. Crying degree adjustment operation 1

Each classified particle group was weighed so that each sample weighed 200 g according to the weight frequency of the particle size distribution shown in Table 2, and various particle sizes were adjusted by mixing with a rocking mixer (manufactured by Aichi Electric) for 2 minutes. A detergent composition was obtained.

According to Evaluations 1-3, the detergent compositions of Examples 1-9 shown in Table 2 were evaluated. As a result, examples 1, 2, 4, 5, and 8 satisfy the equation (1) ∑ (Wi · V i) ≥ 90 () and the weight frequency of the classified particles less than 125 is less than 0.10. It was found that this detergent composition was excellent in solubility, dispersibility and hand wash solubility.

Table 2 Example 1 Example 2 Example 3 1 Example 4 Example 5 1 Example 6 Example 7 Example 8 Example 9

1 Production example 1 Production example 2 Production example 3

(W C1410 ~ 2000 ^ m) 0.00 0.02 0.00 0.00 0.00 0.02 0.03 0.00 0.00 0.01

W C1000 ~ 1410 ^ m] 0.00 0.04 0.00 0.00 0.00 0.03 0.09 0.00 0.00 0.10

W [710-1000〃m] 0.00 0.06 0.00 0.01 0.01 0.06 0.23 0.01 0.01 0.22

W [500-710m] 0.01 0.06 0.01 0.05 0.02 0.07 0.24 0.02 0.06 0.20

W [355-500 zm] 0.09 0.18 0.05 0.20 0.00 0.17 0.19 0.09 0.27 0.13

W [250-355] 0.45 0.38 0.12 0.33 0.00 0.39 0.12 0.15 0.29 0.10

W [180 ~ 250〃m] 0.40 0.16 0.30 0.31 0.00 0.16 0.05 0.24 0.19 0.09

W [125-180〃m] 0.03 0.08 0.35 0.04 0.00 0.08 0.03 0.26 0.10 0.08

W (less than 125 m) 0.02 0.02 0.17 0.03 0.00 0.02 0.02 0.23 0.08 0.07 Uniform particle size (m) 255 330 160 268 220 554 175 309 530 Life span ig / 720 730 650 720 760 780 770 740 748 Roughness (seconds) 6.5 6.8> 10 6.7 6.4 6.2> 10 6.9 6.7

Wi (WiVi) {%] 99.6 93.7 99.7 97.7 95.0 84.9 99.3 95.1 81.5 Value 1 ACA AB BDA AB D 2 II IV III IV Π I 3 [sec] 41 67 38 52 62 100 43 66 111 Example 2

Using the classified particles of the base detergent particles (1) obtained in Production Example 3, the particle size was adjusted according to the following method to obtain the detergent compositions of Examples 10 to 14. Table 3 shows the average particle size, bulk density, fluidity, and ∑ (Wi · Vi) of the obtained detergent composition. Particle size adjustment operation 2

The base detergent particles obtained in Production Example 3 (1) 100 parts were classified with a gyro shifter (manufactured by Tokuju Kosakusho) equipped with a screen of 500 zm, and the particles on the sieve were classified. By removing, 55.1 parts of the detergent composition of Example 10 were obtained. Particle size adjustment operation 3

Example 10 Detergent composition 55.1 As a group of base detergent particles, put into a gyro shifter equipped with a screen having an opening of 125 m to remove fine particles of less than 125 um.Example 1 51.1 parts of the detergent composition of 1 were obtained. Particle size adjustment operation 4

In the same manner as in the particle size adjustment operation 2, 100 parts of the base detergent particles (1) obtained in Production Example 3 were put into a gyrosif equipped with a 500-m mesh screen, and the particles A on the sieve were added. The particles were classified into the undersize sieve particles A. The weight was 44.5 parts and 55.3 parts, respectively. 54.5 parts of this on-screen particle group A2 and 2 parts of powdered zeolite (average particle size: 3 m) as a disintegration aid were put into a Fitzmill (manufactured by Hosoiki Micron) together with cooling air to obtain one-stage disintegrated particles. Was. Then, it was charged into the second-stage Fitzmill to obtain two-stage crushed particles. In the Fitzmill screen, the first stage had a diameter of 2 mm, and the second stage had a diameter of l mm. The average particle size of the two-stage disintegrated particles was 376 um, and 23.2 parts of particles of 500 or more in 46.7 parts of the two-stage disintegrated particles were contained. The two-stage crushed particles are thrown into the gyro shifter on a 500-m screen. And classified into on-sieving particle group B and under-sieving particle group B. This underscreen particle group B25.0 parts and the underscreen particle group A55.5 parts were blended to obtain 80.5 parts of the detergent composition of Example 12.

Particle size adjustment operation 5

Example 12 Detergent composition of Example 13 80.5 parts are introduced into the above gyrosif equipped with a screen of 1 2 5 zm with a screen of 1 2 5 zm and fine particles less than 1 2 5 m are removed, Composition 76.2 2 parts were obtained. Particle size adjustment operation 6

80.5 parts of the detergent composition of Example 12 were charged into a gyro shifter provided with a screen having an opening of 180 zm, and classified into a particle group C on the sieve and a particle group C under the sieve. The on-sieve particle group C and the under-sieve particle group C were 65.1 parts and 15.4 parts.

The undersize particle group C was granulated by the following operation. To the high-speed mixer, 5.4 parts of the undersize particle group C1 were added, and 0.77 parts of the nonionic surfactant was spray-added over 1.3 minutes, followed by stirring and granulating for 10 minutes. Next, 0.92 parts of zeolite (average particle size of about 3 ^ m) was added, and the surface coating treatment was performed for 1 minute to obtain a base detergent particle group (2) (average particle size: 662 fim). Using a gyro shifter with a mesh size of 500 m, this is classified into a particle group A 'on the sieve and a particle group A' under the sieve, and the particle group A 'on the sieve is disintegrated in two stages using Fitzmill. Then, the crushed particles were classified into an on-size particle group B ′ and an under-size particle group B ′ using a gyro sif Yuichi having a mesh size of 500 μm. Then, the undersize particle group B ', the undersize particle group A' and the undersize particle group C were blended to obtain 80.0 parts of the detergent composition of Example 14.

According to Evaluations 1-3, the detergent compositions of Examples 10-14 shown in Table 3 were evaluated. As a result, it was found that all of the detergent compositions of Examples 10 to 14 were excellent in solubility, dispersibility, and hand-washing solubility. Here, the weight of the classified particles of less than 125 / m It was found that the detergent compositions of Examples 1 to 13 having a low degree of dispersion were particularly excellent in dispersibility. Table 3

Test example 1

Representatives sold or previously sold in Asia, Europe, United States Table 4 shows the results obtained by measuring the solubility of the particles and the solubility of the hand washing of the eight detergent compositions. The results in Table 4 show that these commercially available detergents have a low level of particle solubility and are also poor in hand wash solubility. In addition, among the commercially available detergents A to H, A, which has the highest particle solubility and hand wash solubility, had extremely poor fluidity.

Table 4

1) Dense 60 g 1

In the measurement of fluidity, powder 100

The fluidity was so low that almost no ML flowed out.

Industrial applicability

The detergent composition of the present invention dissolves quickly after being poured into water even in cold water, has excellent solubility when used for hand washing, and has excellent dispersibility due to aggregation between particles. It has excellent detergency and solubility even under low mechanical washing conditions like a machine. In the present invention described above, there are various types in the range of obvious identity. Such variations are not considered to depart from the spirit and scope of the invention, and all such changes that are obvious to those skilled in the art are included within the scope of the following claims.

Claims

The scope of the claims

1. It contains 5 to 60% by weight of phosphate builder and 10 to 60% by weight of surfactant, has a bulk density of 600 to 1200 gZL, and has a flow time of 10 seconds or less. A detergent composition with an aperture of 2000 / m. 1410 m, 1000 m, 7100 m, 500 m, 355 m, 25 Weight frequency of each classified particle group obtained by classifying detergent particles using a classifier consisting of sieves of 0 m, 180 μm and 125 μm and a pan, and the measurement shown below. Detergent whose sum of the products of the classified particles and the dissolution rate V i measured under the conditions satisfies the following formula (1), and the weight frequency of the classified particles less than 125 m is 0.10 or less Composition:

∑ (WiVi) ≥ 90 (%) (1)

[Measurement conditions: 5 ° C ± 0.5 ° 〇 hardness 4 ° 011 water 1.00 L ± 0.03 L sample

1. Add 0.000 g ± 0.010 g, and use a cylindrical stirrer (length 35 mm, diameter 8 mm) for 60 seconds in a 1 L beaker (inner diameter 105 mm). After stirring at 800 rpm, the residue is filtered through a standard sieve specified in JISZ8801 (mesh size: 74 nm). The dissolution rate Vi of the classified particles is calculated by the following equation (2). Here, i means each classified particle group.

V i = (1 -T i / S i) X 1 0 0 (%) (2)

(Here, Si represents the input weight (g) of each classified particle group, and Ti represents the dry weight (g) of the dissolved residue of each classified particle group remaining on the screen after filtration.)]

2. After performing a classification operation on the unclassified detergent particles containing 5 to 60% by weight of the phosphate builder and 10 to 60% by weight of the surfactant, each of the obtained classified particles was subjected to classification. The method according to claim 1, further comprising the step of: adjusting the particle size so that the expression (1) according to claim 1 is satisfied and the weight frequency of the classified particles having a particle size of less than 125 / m is 0.10 or less. A method for producing the detergent composition according to the above.