Title of Invention

LAUNDRY CREAMY SMOOTHNESS IMPROVER

Abstract A laundry creamy smoothness improver containing potassium metaphosphate having a viscosity in an aqueous solution of 200 mPa s or more, wherein the viscosity is determined under the specified conditions; a detergent composition containing the laundry creamy smoothness improver as defined above, and a solubilizing agent; a process for hand-washing, wherein washing is carried out under specified conditions; and a process for preparing a potassium metaphosphate as defined above, including the step of spray-drying an aqueous solution of potassium dihydrogenphosphate and phosphoric acid, or an aqueous solution of potassium dihydrogenphosphate, phosphoric acid, a network-forming element other than phosphorus, and/or a network-modifying element other than K, and baking the spray-dried product.
Full Text

DESCRIPTION
LAUNDRY CREAMY SMOOTHNESS IMPROVER
FIELD OF THE INVENTION
The present invention relates to a laundry creamy smoothness improver capable of avoiding cloth damages. More specifically, the present invention relates to an additive in washing on the bases of new technical ideas: The handwashing ability is improved in that washing can be performed with a reduced effort by improving the smoothness between items during hand-washing and that the rate of rubbing the laundry items (number of rubbings per unit time) is likely to be increased, and the damages of the items to be washed due to rubbing between the laundry items and the cut damages and rubbing damages generated on hands due to rubbing hands with each other are suppressed. In addition, the present invention relates to a detergent composition containing the above creamy smoothness improver. Further, the present invention relates to a process for hand-washing in the presence of a potassium metaphosphate. In addition, the present invention relates to a method of avoiding cloth damages by, for instance, increasing smoothness between the fibers against the damages of fibers which are causative of loss of its shape due to mechanical power such as stirring in washing machines.
BACKGROUND OF THE INVENTION
Washing methods can be roughly classified into hand-washing and washing-machine washing. Recently, with the widespread of washing-machines,

washing-machine washing tends to be increased. However, there are still needs for hand-washing from the viewpoint of easy removal of dirt stains and economic advantages.
Therefore, developments have been made on detergents having preferred properties during hand-washings. For instance, Japanese Unexamined Patent Laid-Open No. Hei 10-504056 discloses a method of improving irritability to skin during hand-washing by formulating an anionic surfactant, a cationic surfactant and a nonionic surfactant in a specified ratio. In addition, regarding the control of bubbles, highly foamable surfactants such as LAS and AS for increasing foam; a nonionic surfactant such as polyoxyethylene alkyl ether for regulating bubbles; and soaps for improvement in foam off during rinsing have been generally known. Specifically, Japanese Examined Patent Publication No. Hei 8-13987 discloses a detergent composition having excellent dissolubility, foaming ability and rinsing ability by containing an anionic surfactant, a specified nonionic surfactant and a fatty acid soap in a specified ratio.
However, studies on techniques for improving facilitation of handwashing (smoothness when the items to be washed are rubbed) have not been so far made,
SUMMARY OF THE INVENTION The present invention relates to: [1] a laundry creamy smoothness improver containing potassium metaphosphate having a viscosity in an aqueous solution of 200 mPa*s or more, wherein the viscosity is determined under the following conditions of adding 2 g of potassium metaphosphate to 50 ml of water, stirring the mixture for 1 minute,

adding a solution prepared by dissolving 4 g of sodium tripolyphosphate (commercially available from Shimonoseki Mitsui Chemicals, Inc.) in 50 ml of water, stirring the mixture for 3 hours, and determining a viscosity with a B-type viscometer at 25°C;
[2] the laundry creamy smoothness improver according to the above [1], wherein a network-forming element other than phosphorus is contained in an amount of 0 to 0.7 mmol to 1 kg of potassium metaphosphate, and a network-modifying element other than K is contained in an amount of 0 to 100 mmol; [3] the laundry creamy smoothness improver according to the above [1] or [2], wherein the potassium metaphosphate is obtained by spray-drying an aqueous solution of potassium dihydrogenphosphate and phosphoric acid, or an aqueous solution of potassium dihydrogenphosphate, phosphoric acid, a network-forming element other than phosphorus, and/or a network-modifying element other than K, and baking the spray-dried product;
[4] the laundry creamy smoothness improver according to any one of the above [1] to [3], wherein the laundry creamy smoothness improver is used for hand-washing;
[5] a detergent composition containing the laundry creamy smoothness improver as defined in any one of the above [1] to [4], and a solubilizing agent; [6] the detergent composition according to the above [5], wherein the detergent composition is a laundry powder detergent;
[7] the detergent composition according to the above [5] or [6], wherein the solubilizing agent contains an ion source for substitution in an amount of at least 0.5 times equivalent based on potassium ion in potassium metaphosphate; [8] the detergent composition according to any one of the above [5] to [7],

further containing a surfactant and/or a builder;
[9] the detergent composition according to the above [8], further containing
as a builder a metal ion capturing agent having a calcium ion capturing ability of
100 mg CaC03/g or more in an amount of 5% by weight or more;
[10] the detergent composition according to the above [9], wherein the metal
ion capturing agent is a water-soluble organic substance;
[11] the detergent composition according to any one of the above [5] to [10],
further containing a silicate;
[12] the detergent composition according to any one of the above [5] to [11],
further containing a phosphate;
[13] a process for hand-washing, wherein washing is carried out under
conditions of a concentration of the potassium metaphosphate as defined in any
one of the above [1] to [3] in water of 30 mg/L or more and a liquor ratio of 2 or
more; and
[14] a process for preparing a potassium metaphosphate as defined in the
above [2], including the step of spray-drying an aqueous solution of potassium
dihydrogenphosphate and phosphoric acid, or an aqueous solution of potassium
dihydrogenphosphate, phosphoric acid, a network-forming element other than
phosphorus, and/or a network-modifying element other than K, and baking the
spray-dried product.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a laundry creamy smoothness improver capable of improving smoothness between items to be washed during handwashing, so that washing can be performed with a reduced power, and hand-

washing is facilitated by increasing the rate of rubbing laundry items (number of rubbings per unit time), and further capable of accomplishing a so-called hand-care effect in which the skin after drying after the hand-washing feels soft and smooth, and a so-called laundry item-care, in which loss of its shape due to mechanical power such as stirring in washing machines can be avoided; a creamy smoothness improver for hand-washing; a detergent composition containing these creamy smoothness improvers; and a process for hand-washing in which smoothness is improved when rubbing together the items to be washed with each other in hand-washing.
By using the laundry creamy smoothness improver of the present invention, effects such as smoothness between items to be washed during handwashing is improved, so that washing can be performed with a reduced power, and hand-washing is facilitated by increasing the rate of rubbing items to be washed (number of rubbings per unit time) are exhibited. Also, effects such as a so-called hand-care, which is attained by increasing feel in hand-washing, and a so-called clothes-care can be accomplished.
These and other advantages of the present invention will be apparent from the following description.
As a result of intensive studies by remarking on completely new property "smoothness" when the items to be washed are rubbed together in washing in order to meet the needs of carrying out hand-washing conveniently, the present inventors have found that the above problems can be solved by separately adding a laundry creamy smoothness improver containing a potassium metaphosphate to a detergent composition during hand-washing, or using a detergent composition containing the above laundry creamy smoothness improver. The present

invention has been perfected thereby.

The laundry creamy smoothness improver can be used by mixing the improver with a detergent, or can be directly added separately from the detergent upon washing.
The laundry creamy smoothness improver of the present invention contains a potassium metaphosphate having a specified viscosity. Specific examples thereof include the potassium metaphosphate alone or a mixture of the potassium metaphosphate with other agents.
The potassium metaphosphate will be described later. Also, the other agents as referred to herein may be any substances generally used in a detergent composition without inhibiting the effects of the potassium metaphosphate. For instance, sodium sulfate, zeolite, polyethylene glycol, an alkyl sulfate or the like can be properly used.
The amount of the potassium metaphosphate is preferably from 30 to 100% by weight, more preferably from 50 to 100% by weight of the laundry creamy smoothness improver.
When the laundry creamy smoothness improver having the above constitution is composed of the potassium metaphosphate alone, the potassium metaphosphate can be directly used, or formed into fine powder by pulverization treatment.
Also, when the laundry creamy smoothness improver is a mixture of the potassium metaphosphate with other agents, the laundry creamy smoothness improver can be prepared by mixing these components by a known method.

The laundry creamy smoothness improver of the present invention serves to improve smoothness between items to be washed during hand-washing, thereby facilitating hand-washing, to enhance feel in hand-washing, and to accomplish hand-care as well as laundry item-care. Accordingly, the present invention also relates to a creamy smoothness improver for hand-washing.
The form of the laundry creamy smoothness improver (hereinafter simply referred to as "creamy smoothness improver") is not particularly limited. The form may be any agent forms such as powders, granules, liquids, or slurries/pastes. In order that the smoothness is quickly exhibited to laundry items thoroughly, it is preferable to use the creamy smoothness improver in the form of powder or granule.
It is preferable that the creamy smoothness improver of the present invention is contained in the detergent composition, from the viewpoints of convenience upon use and dissolubility. Here, the above creamy smoothness improver is not limited by a composition, a form, a preparation process of the detergent composition used, and can exhibit its effects in all of the detergent compositions containing a solubilizing agent which will be described later.

One of the significant features of the detergent composition of the present invention resides in that the detergent composition contains the above creamy smoothness improver and a solubilizing agent. Since the detergent composition has the above features, the effects such as the washing liquid in which a detergent composition is dissolved upon washing becomes a lotion-like viscous solution, so that smoothness is also improved between the items to be washed in

hand-washing, whereby washing can be performed with a reduced power, and hand-washing ability such as tendency of increasing the rate of rubbing items to be washed is improved, and further hand-care effects, in which the dried skin after the hand-washing is felt to be tender and smooth, and laundry item-care effects are exhibited.
The amount of the creamy smoothness improver is preferably from 0.1 to 30% by weight, and more preferably from 0.5 to 20% by weight, of the detergent composition.
The detergent composition may be in any forms such as powders, granules, liquids or pastes, or may be molded into an aggregate, a tablet or the like by a secondary processing. In order to quickly exhibit smoothness in the laundry items thoroughly, it is preferable that the detergent composition is in the form of powder or granule.
Even more, the detergent composition is preferably utilized as a laundry powder detergent.
Here, the washing liquid as used herein refers to a liquid for performing washing such as one in which the above detergent composition is dissolved or suspended.
Each of the components used in the present invention will be explained hereinbelow.
1. Potassium Metaphosphate
The potassium metaphosphate usable in the present invention refers to a substance which has a viscosity of its aqueous solution of 200 mPa*s or more,

preferably 250 mPa*s or more, and more preferably 300 mPa#s or more, when the viscosity is determined using the method for determining a viscosity as described later. Since the potassium metaphosphate having a specified viscosity as described above has an advantage of having a remarkably high smoothness, and shows useful performance as the hand-washing detergent, there is an advantage that the amount of the creamy smoothness improver can be reduced by adding the laundry creamy smoothness improver containing the potassium metaphosphate to a detergent blend.
Here, the viscosity of the aqueous potassium metaphosphate is obtained by the steps of adding 2 g of potassium metaphosphate to 50 ml of water, stirring the mixture for 1 minute, adding a solution prepared by dissolving 4 g of sodium tripolyphosphate (commercially available from Shimonoseki Mitsui Chemicals, Inc.) in 50 ml of water, stirring the mixture for 3 hours, and determining a viscosity with a B-type viscometer at 25°C.
The potassium metaphosphate usable in the present invention is generally prepared by the process represented as follows:
nKH2P04 -> (KP03)n + nH20
Specifically, potassium dihydrogenphosphate (KH2P04) is heated to carry out intermolecular dehydration to form a potassium metaphosphate. Manufactured articles of various degrees of polymerization are obtained depending upon factors such as difference in heating temperature and heating time. The higher the temperature of the dehydration reaction, the larger the degree of polymerization. There is a correlation between the degree of polymerization and the smoothness, and the molecular weight of the potassium

metaphosphate is preferably 10000 or more, more preferably 100000 or more, even more preferably 200000 or more, even more preferably 500000 or more, from the viewpoint of improvement in hand-washing ability. The molecular weight of the potassium metaphosphate is preferably 50000000 or less, more preferably 20000000 or less, from the viewpoint of availability.
The potassium metaphosphate is represented by the general formula (KP03)n, and the structure thereof is represented by the following formula:

Here, the potassium metaphosphate has a structure in which P04 tetrahedrons are linked (or polymerized) with each other by sharing an oxygen atom to form a network of polyphosphate anions, and coordinated with a potassium ion to neutralize an electric charge balance of the polyphosphate anions. As shown in the above structure, an element, such as phosphorus, for forming the network of polyphosphate anions is referred to as a "network-forming element," and an element, such as potassium, for regulating an electric charge of the network of polyphosphate anions is referred to as a "network-modifying element."
The potassium metaphosphate usable in the present invention may contain a network-forming element other than phosphorus in a specified amount and a network-modifying element other than potassium in a specified amount. The network-forming element other than phosphorus or the network-modifying

element other than potassium may be contained in the raw material for potassium metaphosphate or included during the preparation processes.
It is well known that the potassium metaphosphate can be used as a builder for detergents. In such an application, there are no limitations on the network-forming element other than phosphorus or the network-modifying element other than potassium, and the performance as a builder would not be seriously impaired regardless of the ratio of the components. On the other hand, the potassium metaphosphate used in the application of the present invention has a special situation in which the favorable performance can be exhibited in the present invention only when the contents of those elements are restricted to a specified range.
A further phosphorus source of an industrially applicable phosphate compound which is used as raw materials for the potassium metaphosphate includes a so-called phosphate ore produced from nature, which contains calcium phosphate in a large amount, and the like. The phosphate ore mined from nature is industrially derived to a phosphate compound such as phosphoric acid (or a phosphate) through the form of yellow phosphorus, phosphorus oxide or the like. When the purification steps are not included in the process or purification is not satisfactorily carried out, the phosphate compound derived from the mined phosphate ore contains in a large amount the network-forming element other than phosphorus, such as arsenic, which is carried over from the phosphate ore mined. It is a general practice not to perform high-level purification for an inexpensive and industrial-grade phosphate compound for detergent applications and the like, so that the phosphate compound contains the network-forming element other than phosphorus in a large amount. The content of the network-

forming element other than phosphorus varies depending on the difference of fields of phosphate ore or processing processes therefor. Generally, a commercially available industrial-grade phosphate compound contains several dozens to 100 ppm by weight of the network-forming element other than phosphorus.
On the other hand, an industrially applicable potassium source as another raw material for the potassium metaphosphate includes potassium hydroxide obtained by electrolysis of potassium chloride. Potassium chloride is obtained by industrial precipitation method from a mixture containing impurity, such as carnallite, kainite, sylvite, or Halzsalz. The industrial-grade potassium chloride, however, contains other components which cannot be removed by a precipitation method, such as sodium chloride or magnesium chloride, in a large amount. Since these components other than potassium chloride are carried over to the potassium hydroxide obtained after electrolysis, the industrial-grade potassium hydroxide contains a network-modifying element other than potassium in a large amount.
One of ordinary skill in the art who performs a whole or part of a series of phosphorus-processing processes for preparing a phosphate compound from phosphate ore, without almost any exceptions, produce a manufactured article other than potassium phosphate compounds which can serve as a raw material for the potassium metaphosphate. For the purpose of effectively utilizing their facilities, it is in general practice that those individuals who process phosphorus share processing facilities such as a reaction pot, a drying machine and a baking furnace in, for example, the processing of a sodium phosphate compound derived from a phosphoric acid source and a sodium source, the preparation of a

potassium phosphate compound which can serve as a raw material for the potassium metaphosphate, or the preparation of the potassium metaphosphate itself. When the facility and process control, such as the order of the kinds prepared and the processing equipment cleaning when the kinds of the manufactured products are changed, is not adequately carried out, it results in an increase in the components unfavorable in the application of the present invention in the processing steps even if all of various raw materials favorable for the potassium metaphosphate of the present invention were furnished.
Various raw materials for preparing the potassium metaphosphate of the present invention are studied in detail on components other than phosphorus and potassium. It is preferable that the components are subjected to purification or other means in some cases. For example, as an example of a case where the network-forming element other than phosphorus is contained in a preferred range, it is preferable to use a potassium phosphate compound such as potassium dihydrogenphosphate which is highly purified and supplied as a food additive in the preparation of the potassium metaphosphate of the present invention.
The network-forming element other than phosphorus or the network-modifying element other than potassium is incorporated into the potassium metaphosphate to exhibit the same level of performance as phosphorus or potassium and to satisfactorily exhibit the desired performance for the potassium metaphosphate of the present invention, as long as the element is contained in a proper amount. The network-forming element other than phosphorus is not particularly limited, and exemplified by B, As, Si, Ge, Sb, Ti, Sn, Al, Zr and the like. The content of the network-forming element (NWF) is preferably from 0 to

0.7 mmol, more preferably from 0.0001 to 0.4 mmol, and even more preferably from 0.0002 to 0.1 mmol, per 1 kg of the potassium metaphosphate.
The network-modifying element other than potassium is not particularly limited, and exemplified by Fe, Mg, Ni, Zn, Co, Ca, Sr, Ba, Li, Na, Rb, Cs and the like. The content of the network-modifying element (NWM) is preferably from 0 to 100 mmol, more preferably from 0.0001 to 75 mmol, or even more preferably 0.0002 to 25 mmol, per 1 kg of the potassium metaphosphate.
The content of the above network-forming element or network-modifying element refers to a value determined by an atomic absorption spectrometer or an inductively coupled plasma (ICP) emission spectrometer as mentioned herein after.
In addition, in the present invention, the molar ratio of potassium to phosphorus (hereinafter referred to as K/P ratio) is not particularly limited, and the molar ratio is preferably less than 1, more preferably from 0.999 to 0.94, and even more preferably from 0.99 to 0.98. When the K/P ratio is less than 1, polyphosphate anions in the potassium metaphosphate are allowed to form a cross-linking structure as shown the following formula:

thereby undergoing structural transformation from a one-dimensional chain polymer to two-dimensional layered polymer, which gives some advantages that

the polymerization degree is further increased, and an even higher smoothness can be more easily exhibited. Here, the K/P molar ratio can be determined according to the method described in Examples set forth below.
The amount of the potassium metaphosphate of the detergent composition is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, even more preferably 3 parts by weight or more, even more preferably 5 parts by weight or more, even more preferably 7 parts by weight or more, and even more preferably 10 parts by weight or more, based on 100 parts by weight of the detergent composition, from the viewpoint of improvement in handwashing ability. In addition, the amount of the potassium metaphosphate of the detergent composition is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the detergent composition, from the viewpoint of maintaining easy handling of the items to be washed after washing.
In addition, when a washing liquid is prepared by dissolving a detergent composition in water, the concentration of the potassium metaphosphate in water is preferably 15 mg/L or more, more preferably 30 mg/L or more, and even more preferably 60 mg/L or more, from the viewpoint of obtaining excellent handwashing ability. Also, the concentration is preferably 3000 mg/L or less, more preferably 1500 mg/L or less, and even more preferably 1000 mg/L or less, from the viewpoint of easy handling of the items to be washed after washing. It is preferable that the above concentration of potassium metaphosphate in water is increased according to the lowering of the liquor ratio, which is a weight ratio of water to laundry items, i.e. weight of water/weight of laundry items, the increase in the water hardness of the washing liquid, and the increase in the amount of the

nonionic surfactant in the detergent composition and the increase in the ratio to the amount of the nonionic surfactant and the entire surfactant components of the detergent composition.
Next, a process for preparing the potassium metaphosphate will be explained. The potassium metaphosphate can be obtained by subjecting potassium dihydrogenphosphate to dehydration condensation at a high temperature as mentioned above. In the present invention, the potassium metaphosphate is obtained by mixing potassium dihydrogenphosphate and phosphoric acid, and then subjecting the mixture to dehydration condensation at a high temperature in order to adjust the K/P ratio.
It is preferable that potassium dihydrogenphosphate and phosphoric acid are homogeneously mixed with each other. The potassium metaphosphate melts at a temperature of 800°C or higher, to give a molten solution. When the preparation is carried out at a temperature of 800°C or higher to give a molten state, homogeneous mixing is achieved by diffusion of liquids. However, when the preparation is carried out at a temperature of 800°C or lower, since the reaction takes place in a solid state, it is preferable that the raw materials are homogeneously mixed in advance and then the mixture is baked from the viewpoint of smoothness. As a specific example of mixing raw materials, since both of potassium dihydrogenphosphate and phosphoric acid are water-soluble, a process including the steps of mixing these components to form a homogeneous aqueous solution, and spray-drying the aqueous solution is preferred. An example of mixing an aqueous solution containing a phosphorus source such as phosphoric acid or an aqueous solution containing a potassium source such as potassium hydroxide in a preferred ratio is essentially same as the above process

to achieve the effect of the present invention. Alternatively, potassium dihydrogenphosphate in the form of powder may be supplied into a mixer rotated at a high speed, and phosphoric acid in the form of liquid is sprayed or dropped thereto. The mixer is preferably a solid mixer, and exemplified by, for example, a horizontal cylindrical mixer, a V-blender, a double cone mixer, a Ribbon Mixer, a conical screw mixer, a high speed mixer, a rotary disk mixer, a fluidized mixer, a free fall mixer, an agitation mixer and the like. Among them, preferable is the high-speed mixer which is capable of performing an even more homogeneous mixing by high-speed mixing. Furthermore, according to the process including the steps of dissolving potassium dihydrogenphosphate in water, mixing the solution with phosphoric acid, and then subjecting the mixture to spray-drying, a mixed powder in which potassium dihydrogenphosphate and phosphoric acid are even more uniformly mixed is obtained.
The above aqueous solution prepared by mixing potassium dihydrogenphosphate and phosphoric acid, for example, may contain a network-forming element other than phosphorus and/or a network-modifying element other than potassium from the viewpoint of smoothness of the potassium metaphosphate obtained.
The baking temperature at which the condensation reaction is carried out, is preferably 400°C or higher, more preferably 500°C or higher, and even more preferably 600°C or higher, from the viewpoint of smoothness after the immersion, and the baking temperature is preferably 1500°C or lower, more preferably 1300°C or lower, even preferably 1200°C or lower, and even more preferably 800°C or lower, from the viewpoint of energy consumption.

The potassium metaphosphate obtained by baking is preferably pulverized with a pulverizer to a particle size that can easily exhibit an effect of smoothness in a detergent blend.
As the particle size of the potassium metaphosphate, the average particle size is preferably 100 μm or more, more preferably 150 μm or more, and even more preferably 200 μm or more, from the viewpoint of maintaining an effect of improving hand-washing ability, and the average particle size is preferably less than 500 μm, more preferably less than 400 μm, or even more preferably less than 300 μm, from the viewpoint of dissolubility (suppression of deposition insoluble remnants or deposition to clothes). In addition, when the potassium metaphosphate is blended to form the granules, the average particle size is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 5 μm or more, even more preferably 10 μm or more, and even more preferably 30 μm or more, from the viewpoint of handling ability, and the average particle size is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less, from the viewpoint about granulating ability.
The method for adjusting the average particle size of the potassium metaphosphate within the above range includes a method including the step of subjecting the potassium metaphosphate to pulverization treatment with a known pulverizer such as Atomizer commercially available from Fuji Paudal Co., Ltd, Pin Mill commercially available from Hosokawa Micron Corporation and Turbo Mill commercially available from TURBO KOGYO CO., LTD.
2. Solubilizing Agent
The potassium metaphosphate is extremely hardly soluble in water, but

shows water solubility in the presence of a solubilizing agent. The solubilizing agent as used herein refers to a compound containing a sodium ion source and/or a lithium ion source and/or an ammonium ion source, wherein the sources can substitute potassium of the potassium metaphosphate. Therefore, in the detergent composition, by using the above creamy smoothness improver containing the potassium metaphosphate, together with a solubilizing agent, the potassium metaphosphate dissolves even when the detergent composition is dissolved in water, so that the washing liquid becomes a lotion-like viscous solution, whereby consequently giving advantages such as smoothness between the items to be washed is improved, and the hand-washing is improved.
The above solubilizing agent includes all those sodium ion sources and/or lithium ion sources and/or or ammonium ion sources which replace potassium of the potassium metaphosphate. Even more useful solubilizing agents are inorganic salts and organic salts of sodium, lithium and ammonium, including, for instance, sodium carbonate, sodium chloride, sodium sulfate, sodium sulfite, sodium carboxylates such as sodium citrate, sodium phosphate, sodium silicate, sodium salts of polycarboxylic acids, sodium salts of polysulfonic acids, lithium halides and lithium sulfate. Among them, inorganic salts and organic salts of sodium are even more preferable. In addition, a salt form of a surfactant or a fatty acid, a metal ion capturing agent or the like can also serve as a solubilizing agent.
Since the above potassium metaphosphate shows water solubility by replacing potassium ion in the potassium metaphosphate with sodium ion and/or lithium ion and/or ammonium ion, it is desired to use the potassium metaphosphate in a state that can be dissolved in order to obtain an excellent

hand-washing ability. Although some effects can be exhibited if a part of potassium in the potassium metaphosphate can be replaced, it is preferable that the amount of the solubilizing agent is one that can supply sodium ions and/or lithium ions and/or ammonium ions in an amount that can completely replace potassium ions in the potassium metaphosphate contained in the washing liquid from the viewpoint of economic advantages. The amount of the solubilizing agent is preferably 0.5 times equivalent or more, more preferably 1 time equivalent or more, even more preferably 2 times equivalent or more, and even more preferably 3 times equivalent or more, when the amount that can supply sodium ions and/or lithium ions and/or ammonium ions in the same amount as that of potassium ions in the potassium metaphosphate is defined as 1 time equivalent. On the other hand, there is a little effect of improving hand-washing ability in the presence of excess sodium ions and/or lithium ions and/or ammonium ions to the potassium ions. From this viewpoint, the amount of the solubilizing agent is preferably 400 times equivalent or less, more preferably 200 times equivalent or less, and even more preferably 100 times equivalent or less. In addition, the amount of the solubilizing agent is preferably 30 times equivalent or less, and more preferably 20 times equivalent or less, from the viewpoint of even more maintaining the effect of improving smoothness.
Incidentally, when necessary amounts of sodium ions and/or lithium ions and/or ammonium ions are formulated in the detergent composition for other purposes, it is not necessary to separately add a solubilizing agent to the detergent composition.
3. Surfactant and/or Builder

The detergent composition of the present invention can contain a surfactant and/or a builder.
As the surfactant, those generally used for detergents can be used. The surfactant includes, for instance, anionic surfactants and nonionic surfactants. Examples of the surfactant include anionic surfactants such as alkylbenzenesulfonates, alkyl ether or alkenyl ether sulfates, alkyl or alkenyl sulfuric esters, ct-olefinsulfonates, alkanesulfonates, N-acylamino acid-type surfactants, alkyl ether or alkenyl ether carboxylates, amino acid-type surfactants, alkyl or alkenyl phosphoric esters, or salts thereof; and nonionic surfactants such as polyoxyalkylene alkyl (or alkenyl) ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts, sucrose fatty acid esters, alkyl glycosides and fatty acid glycerol monoesters.
Among them, alkylbenzenesulfonates, alkyl ether sulfates, alkyl sulfuric esters are preferable, and alkylbenzenesulfonates are even more preferable, from the viewpoint of enhancing the effect of smoothness.
The content of the above anionic surfactant and the nonionic surfactant is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 12% by weight or more, even more preferably 15% by weight or more, and even more preferably 17% by weight or more, of the detergent composition, from the viewpoint of washing performance. In addition, the content of the above anionic surfactant and the nonionic surfactant is preferably 40% by weight or less, more preferably 35% by weight or less, even more preferably 30% by weight or less, and even more preferably 26% by weight or less, of the detergent composition, from the viewpoint of powder properties.
In the detergent composition of the present invention, there can be further

formulated a surfactant such as a betain-type amphoteric surfactant, a phosphoric ester-based surfactant, a soap, or an cationic surfactant in a proper amount.
The builder includes metal ion capturing agents, alkalizing agents, anti-redeposition agents and the like.
Among them, since there is a feature of lowering the effect of improving smoothness with the elevation of the amount of the water hardness-increasing component in the washing liquid, it is very effective to formulate a metal ion capturing agent in the detergent composition as a builder and to capture the water hardness-increasing component in the washing liquid for exhibiting the properties of the potassium metaphosphate. Even more, those metal ion capturing agents having a calcium ion capturing ability of 100 mg CaC03/g or more are more effective. The metal ion capturing agent includes ion exchange materials such as zeolites and crystalline silicates; water-soluble organic substances such as polymers such as polyacrylates and acrylic acid-maleic acid copolymers (salts); and chelating agents such as sodium tripolyphosphate, ethylenediaminetetraacetates, methylglycinediacetates and citrates.
Potassium metaphosphate, sodium carbonate and amorphous sodium silicate are not included in the metal ion capturing agent.
The alkalizing agent includes carbonates and silicates. Amorphous sodium silicate is preferable from the viewpoint of enhancing the effect of smoothness.
The anti-redeposition agent includes carboxymethyl cellulose, polyethylene glycols and the like.
The amount of the builder formulated is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or

more, and even more preferably 20% by weight or more, of the detergent composition, from the viewpoint of improving hand-washing ability. In addition, the amount of the builder formulated is preferably 60% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less, of the detergent composition, from the viewpoint of the balance of the formulation.
4. Silicates and Phosphates (excluding potassium metaphosphate)
The detergent composition of the present invention may contain a silicate or a phosphate, thereby giving an advantage that the effects of improving smoothness can be further improved.
As the silicates, amorphous and crystalline silicates have been known, and any of those can be used. It is desired that those silicates having an Si02/M20 molar ratio, wherein M is an alkali metal, of preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more, and those silicates having an Si02/M20 molar ratio of preferably 4 or less, and more preferably 3 or less. Here, the even more preferable silicates are amorphous silicates, and JIS No. 1 Sodium Silicate or JIS No. 2 Sodium Silicate can be suitably used. The amount of the silicate formulated is preferably 3% by weight or more, more preferably 5% by weight or more, and even more preferably 7% by weight or more, of the detergent composition, from the viewpoint of hand-washing ability. In addition, the amount of the silicate formulated is preferably 30% by weight or less, and more preferably 20% by weight or less, of the detergent composition, from the viewpoint of suppressing the insoluble remnants during washing while maintaining an effect of improving smoothness at a high level.

The phosphate includes sodium tripolyphosphate, sodium pyrophosphate, sodium dihydrogenphosphate, sodium hydrogenphosphate, sodium phosphate and the like, and sodium tripolyphosphate is preferred. The amount of the phosphate formulated is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more, of the detergent composition, from the viewpoint of hand-washing ability. In addition, the amount of the phosphate formulated is preferably 40% by weight or less, and more preferably 30% by weight or less, of the detergent composition, from the viewpoint of satisfying both of an effect of improving smoothness and detergency.
In the present invention, among the above components, since the metal ion capturing agent, the silicate and the phosphate are formulated in amounts mentioned above, there is an advantage that hand-washing ability is excellently maintained even when the amount of the potassium metaphosphate formulated is reduced.
5. Other Additives
In the detergent composition of the present invention, there can be formulated an enzyme, a perfume, a fluorescer, a pigment or the like in a proper amount.
6. Process for Preparing Detergent Composition
The detergent composition of the present invention having the constitution as mentioned above can be prepared by appropriately blending each of the above-mentioned components by a known method.

Incidentally, since the potassium metaphosphate contained in the detergent composition of the present invention shows water solubility in the presence of the solubilizing agent in water as mentioned above, it is preferable to reduce the water content during the preparation process and during storage. For instance, when the detergent composition is prepared by a spray-drying method, it is desired that the creamy smoothness improver and/or creamy smoothness improver granules are added in the granulation step, the surface modification step, the after-blending step or the like after the spray-drying step.
In addition, when a washing liquid is prepared by separately adding a detergent composition containing components except for the creamy smoothness improver during hand-washing, and a creamy smoothness improver, it is preferable to use a mixture of the potassium metaphosphate with other agents as the creamy smoothness improver for the purpose of suppression of the generation of doughy mass during the dissolution.
In addition, the solubilizing agent may be contained in the creamy smoothness improver and/or creamy smoothness improver granules and/or in the detergent composition, so that the solubilizing agent is not necessarily contained in the detergent composition.
Examples of the detergent composition include those detergent compositions having the compositions and prepared by a process described in Tokkyocho Koho: Shuchi Kanyo Gijutsu Shu (Clothes Powder Detergent: Japanese Patent Office), 10(1998)-25(7159).
7. Process for Washing
The process for washing of the present invention is a process including

the step of carrying hand-washing under the conditions of a concentration of a potassium metaphosphate in water of 30 mg/L or more and a liquor ratio of 2 or more. The process includes, for instance, a process including the steps of adding a potassium metaphosphate to a washing liquid as a part of detergent components or separately from the detergent components, and carrying out hand-washing; and the like.
Specific embodiments include a process including the step of adding the above creamy smoothness improver to a washing liquid as a part of detergent components or separately from the detergent components, and carrying out handwashing.
In the present invention, since the concentration of the potassium metaphosphate in water and the liquor ratio are adjusted to specified ranges as mentioned above, there are some advantages that the washing liquid becomes a lotion-like viscous liquid, so that the improvement in the smoothness between the items to be washed is felt, and that dissolubility of the potassium metaphosphate and its adsorption to the surface of the items to be washed are accelerated, with the increase in the liquor ratio, so that the improvement of the smoothness between the items to be washed is realized.
The concentration of the potassium metaphosphate in water is preferably 15 mg/L or more, more preferably 30 mg/L or more, and even more preferably 60 mg/L or more, from the viewpoint of improving smoothness. In addition, the concentration of the potassium metaphosphate is preferably .3000 mg/L or less, more preferably 1500 mg/L or less, and even more preferably 1000 mg/L or less, from the viewpoint of easy handling of the items to be washed after washing. In addition, it is preferable that the concentration of the potassium metaphosphate in

water is increased according to the lowering of the liquor ratio, the increase in the water hardness of the washing liquid, and the increase in the amount of the nonionic surfactant and the increase in the ratio to the amount of the nonionic surfactant and the entire surfactant components of the detergent composition. In addition, the liquor ratio, which is a weight ratio of water to laundry items is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more, from the viewpoints of dissolubility and adsorption to items to be washed. The liquor ratio is preferably 20 or less, and more preferably 15 or less, from the viewpoint of easy handwashing.
By using the process for washing of the present invention having the constitution as described above, effects such as the smoothness can be improved when the items to be washed are rubbed with each other during hand-washing, and washing can be performed in a reduced power and rate of rubbing laundry items (number of times of rubbing per unit time) is increased, so that feel in hand-washing is improved, whereby accomplishing hand-care, are exhibited. In addition, by using the process for washing of the present invention, cloth damages can be avoided by increasing smoothness between the fibers against the damages of fibers which are causative of loss of its shape in mechanical power such as stirring in washing with a washing machine as well as hand-washing, whereby a so-called "laundry item-care effects" can be exhibited.
EXAMPLES
The following examples further describe and demonstrate embodiments of

the present invention. The examples are given solely for the purposes of illustration and are not to be construed as limitations of the present invention.
The determination methods for the properties in Examples will be described hereinbelow.

Two grams of a potassium metaphosphate was added to 50 ml of water, and the mixture was stirred for 1 minute. Thereafter, a solution prepared by adding 4 g of sodium tripolyphosphate (manufactured by Shimonoseki Mitsui Chemicals, Inc.) to 50 ml of water was added to the mixture, and the resulting mixture was stirred for 3 hours. The viscosity of the resulting mixture was determined at 25 °C with a B-type viscometer.

A 0.1 g sample was dissolved in water, and 4 ml of an aqueous HC1 (1:1) was added thereto to make up a total volume of 50 ml. The content of Na in the sample was determined using this solution with an atomic absorption spectrometer (commercially available from VARIAN, Atomic Absorption Spectrometer Spectra AA220).

A 5 g sample was dissolved in water, and 4 ml of an aqueous HC1 (1:1) was added thereto to make up a total volume of 50 ml. The content of As in the sample was determined using this solution with an inductively coupled plasma

emission spectrometer (commercially available from HORIBA JOBINYVON, JY238ULTRAACE).

A 0.1 g sample was placed in a platinum crucible, and 5 g of Li2B407 and 0.5 g of a stripping agent (Li2C03: LiBr : LiN03 = 5 :1:1 in a weight ratio) were further added thereto. The mixture was melted at 1230°C with a bead-sampler (commercially available from Tokyo Kagaku K.K., NT-2100) to give glass beads.
K and P in the glass beads were determined with a fluorescent X-ray analyzer (commercially available from Rigaku Corporation, ZSXlOOe) under the following conditions (XRF intensity):
X-ray source : Rh tube
Voltage, electric current: 50 kV, 50 mA
Spectral Crystal Detector Angle
- K: LiF SC (scintillation counter) 136.68 deg
- P : Ge PC (proportional counter) 141.19 deg
The calculation of the K/P molar ratio was made by obtaining the values for KH2PO4 (commercially available from Sigma-Aldrich Japan K.K., reagent special grade) in the same manner as that of the samples, and calculating a K/P molar ratio of the samples according to the following formula using a K/P molar ratio of 1.00 as a standard:

K/P Molar Ratio =
[XRF Intensity of K (sample) X XRF Intensity of P (reagent)]/ [XRF Intensity of P (sample) X XRF Intensity of K (reagent)]
Conditions for Hand-Washing
A 8.2 L polypropylene washtub (manufactured by YAZAKI) having a diameter of 30 cm and a depth of 13 cm was charged with 2 liters of hard water (Ca/Mg molar ratio: 7/3) corresponding to 89.3 mg CaCO3/liter, temperature-controlled to 25°C, and a detergent composition weighed so as to be 8.48 g was supplied into the water, and the water was continued to be stirred by hand with a vigorousness that the water was not spilled from the washtub. After 30 seconds from the beginning of stirring, a 100% cotton T-shirt (white, manufactured by Gunze, L size) was soaked in the washing liquid in the washtub so that an entire T-shirt is sufficiently soaked. Thereafter, the breast portions of the T-shirt were held with both hands from the back side of the T-shirt, and the breast portions of the T-shirt were rubbed with each other. The portions were rubbed together upon taking the shirt out of the washing liquid. After rubbing together for every 3 to 5 times, the rubbed portions were temporarily soaked in the washing liquid. The easiness in rubbing when the portions were rubbed together is judged in Ranks 1 to 5 as smoothness. When this evaluation was carried out only with the water prepared above, the wrinkles of the T-shirt hinder the smoothness, the portions to be rubbed together were hardly likely to be rubbed because there are no bubbles in the portions rubbed together, so that the smoothness was worsened.

In such a case, the smoothness is defined to have a rank of 1. The state of each
rank is as follows.
Rank 1: very low smoothness and some feel of squeakiness, thereby making
it very difficult to perform hand-washing.
Rank 2: low smoothness and some feel of squeakiness, thereby not easily
performing hand-washing.
Rank 3: smoothness being medium level, and being capable of performing
hand-washing without squeakiness.
Rank 4: smoothness being high, being capable of performing hand-washing
more easily without squeakiness.
Rank 5: smoothness being very high, being capable of performing hand-
washing very easily without squeakiness.
Incidentally, in the above test, an average value of the evaluation results of 6 panelists are obtained to give the rank.
(Example 1)
(1) Preparation of Potassium Metaphosphate
The amount 28.8 g of the raw material KH2P04 containing Na and As in amounts shown in Table 1 was dissolved in 360 g of ion-exchanged water. Thereafter, 0.488 g of H3P04 (commercially available from Wako Pure Chemical Industries, Ltd., reagent special grade, purity 85%) was added to the solution so as to have a K/P ratio of 0.98, and the mixture was stirred. The resulting mixed solution was spray-dried by a spray dryer (commercially available from TOKYO RIKAKIKAI CO., LTD., "Spray Dryer Model SD-1000") to give a powder.

Ten grams of the powder obtained was placed in an alumina crucible, and baked at 700°C for 3 hours. The obtained product was pulverized in a mortar to give each of powders of a potassium metaphosphate containing Na and As in amounts shown in Table 1 (1-1 to 1-10). The determination results for viscosities of these potassium metaphosphates are shown in Table 1.
(2) The amount 370 kg of the preparation water for the detergent composition, 200 kg of a 50% by weight aqueous sodium dodecylbenzenesulfonate, 50 kg of a 40% by weight aqueous No. 2 silicate, 100 kg of sodium carbonate, 147.5 kg of sodium sulfate, 5 kg of polyethylene glycol, 2.5 kg of a CBS fluorescer, and 125 kg of zeolite were mixed together, to give a homogeneous slurry. Thereafter, the obtained slurry was spray-dried, to give a powder. The amount 0.48 g of the potassium metaphosphate (1-1 to 1-10) prepared by the above method was mixed with 8 g of the resulting powder, to give a detergent composition. This detergent composition was subjected to the hand-washing evaluation. The results are shown in Table 1.
(Comparative Example 1)
Each of the potassium metaphosphates (1-1 to 1-6) were prepared in the same manner as in Example 1 using a raw material KH2P04 containing Na and As in amounts shown in Table 2, to give each of detergent compositions. The determination results for viscosities of the potassium metaphosphate and the evaluation results for hand-washing of the detergent composition are shown in Table 2.





It can be seen from the comparison between Example 1 and Comparative Example 1 that when the content of Na, a network-modifying element, in the potassium metaphosphate is from 0 to 100 mmol and the content of As, a network-forming element, is from 0 to 0.7 mmol, the detergent compositions having high viscosities and excellent hand-washing evaluation results are obtained.
(Example 2)
A potassium metaphosphate without containing Na and As (K/P ratio: 0.98) was prepared in the same manner as in Example 1 using KH2P04 (commercially available from Sigma-Aldrich Japan K.K., reagent special grade) without containing Na and As, to give a detergent composition. Thereafter, the determination of viscosity and the hand-washing evaluation were carried out in the same manner as in Example 1. As a result, the viscosity was 450 mPa*s, and the hand-washing evaluation results were ranked 4.
(Example 3)
The amount 28.8 g of KH2P04 (commercially available from Sigma-Aldrich Japan K.K., reagent special grade) without containing Na and As was dissolved in 360 g of ion-exchanged water. The amount 0.0066 g of CaCl2 (commercially available from Wako Pure Chemical Industries, Ltd., reagent special grade) was added to the solution, and thereafter 0.488 g of H3P04 (commercially available from Wako Pure Chemical Industries, Ltd., reagent special grade, purity: 85%) was added thereto so as to adjust its K/P ratio to 0.98, and the mixture was stirred. This solution was spray-dried and baked in the

same maimer as in Example 1, to give a potassium metaphosphate having a content of Ca, a network-modifying element, of 83 mmol (K/P ratio: 0.98). Subsequently, a detergent composition was obtained. The viscosity of the potassium metaphosphate was 630 mPa*s, and the hand-washing evaluation results were ranked 5.
(Example 4)
The amount 28.8 g of KH2P04 (commercially available from Sigma-Aldrich Japan K.K., reagent special grade) without containing Na and As was placed in an alumina crucible. The amount 0.488 g of H3PO4 (commercially available from Wako Pure Chemical Industries, Ltd., reagent special grade, purity 85%) was dropwise added to the crucible so as to have a K/P ratio of 0.98, and the mixture was stirred. The mixture was baked and pulverized in the same manner as in Example 1, to prepare a potassium metaphosphate without containing Na and As (K/P ratio: 0.98). Subsequently, a detergent composition was obtained.
The determination for viscosity and the hand-washing evaluation were carried out in the same manner as in Example 1. As a result, the viscosity was 250 mPa*s and the hand-washing evaluation results were ranked 3.
When the potassium metaphosphate of this example was compared with the potassium metaphosphate of Example 2, which was prepared by spray-drying a mixed aqueous solution of raw materials, the mixing was unsatisfactory, the viscosity was low and the hand-washing evaluation results were somewhat worse.
In addition, when the potassium metaphosphates of Example 3 and 4 were compared, the potassium metaphosphate containing 83 mmol of the network-

modifying element (Example 3) gave more favorable hand-washing evaluation results.
In the hand-washing in Example 1 to 4, there were no rough skins on hands, thereby showing excellent hand-care. The state of T shirts after the handwashing evaluation for Example 1 to 4 was examined. As a result, it can be seen that frayed fibers and the like were not generated in any of the examples, thereby also showing excellent clothes-care.
The present invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.







CLAIMS
1. A laundry creamy smoothness improver comprising potassium metaphosphate having a viscosity in an aqueous solution of 200 mPa s or more, wherein the viscosity is determined under the following conditions of adding 2 g of potassium metaphosphate to 50 ml of water, stirring the mixture for 1 minute, adding a solution prepared by dissolving 4 g of sodium tripolyphosphate (commercially available from Shimonoseki Mitsui Chemicals, Inc.) in 50 ml of water, stirring the mixture for 3 hours, and determining a viscosity with a B-type viscometer at 25 °C.
2. The laundry creamy smoothness improver according to claim 1, wherein a network-forming element other than phosphorus is contained in an amount of 0 to 0.7 mmol to 1 kg of potassium metaphosphate, and a network-modifying element other than K is contained in an amount of 0 to 100 mmoL
3. The laundry creamy smoothness improver according to claim 1 or 2, wherein the potassium metaphosphate is obtained by spray-drying an aqueous solution of potassium dihydrogenphosphate and phosphoric acid, or an aqueous solution of potassium dihydrogenphosphate, phosphoric acid, a network-forming element other than phosphorus, and/or a network-modifying element other than K, and baking the spray-dried product.
4. The laundry creamy smoothness improver according to any one of claims 1 to 3, wherein the laundry creamy smoothness improver is used for hand-

washing.
5. A detergent composition containing the laundry creamy smoothness improver as defined in any one of claims 1 to 4, and a solubilizing agent.
6. The detergent composition according to claim 5, wherein the detergent composition is a laundry powder detergent.
7. The detergent composition according to claim 5 or 6, wherein the solubilizing agent comprises an ion source for substitution in an amount of at least 0.5 times equivalent based on potassium ion in potassium metaphosphate.
8. The detergent composition according to any one of claims 5 to 7, further comprising a surfactant and/or a builder.
9. The detergent composition according to claim 8, further comprising as a builder a metal ion capturing agent having a calcium ion capturing ability of 100 mg CaC03/g or more in an amount of 5% by weight or more,
10. The detergent composition according to claim 9, wherein the metal ion capturing agent is a water-soluble organic substance.
11. The detergent composition according to any one of claims 5 to 10, further comprising a silicate.

12. The detergent composition according to any one of claims 5 to 11, further
comprising a phosphate.
13. A process for hand-washing, wherein washing is carried out under
conditions of a concentration of the potassium metaphosphate as defined in any
one of claims 1 to 3 in water of 30 mg/L or more and a liquor ratio of 2 or more.
14. A process for preparing a potassium metaphosphate as defined in claim 2,
comprising the step of spray-drying an aqueous solution of potassium
dihydrogenphosphate and phosphoric acid, or an aqueous solution of potassium
dihydrogenphosphate, phosphoric acid, a network-forming element other than
phosphorus, and/or a network-modifying element other than K, and baking the
spray-dried product.


Documents:


Patent Number 248883
Indian Patent Application Number 2516/CHENP/2007
PG Journal Number 36/2011
Publication Date 09-Sep-2011
Grant Date 05-Sep-2011
Date of Filing 11-Jun-2007
Name of Patentee KAO CORPORATION
Applicant Address 14-10, NIHONBASHI KAYABACHO 1-CHOME, CHUO-KU, TOKYO 103-8210.
Inventors:
# Inventor's Name Inventor's Address
1 OKI, KAZUO c/o,KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA 640-8580.
2 KASAI, KATSUHIKO c/o,KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA 640-8580, JAPAN
3 WARITA, HIROAKI c/o,KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA 640-8580, JAPAN
4 TANNO, MAKOTO c/o,KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA 640-8580, JAPAN
5 YAMAGUCHI, SHU c/o,KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA 640-8580, JAPAN
PCT International Classification Number C11D 3/06
PCT International Application Number PCT/JP2005/020785
PCT International Filing date 2005-11-08
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-327912 2004-11-11 Japan