WO2004101721A2

WO2004101721A2 - A sliding property improver for use in washing

Info

Publication number: WO2004101721A2
Application number: PCT/JP2004/006872
Authority: WO
Inventors: Hiroaki Warita; Yoshinobu Imaizumi; Katsuhiko Kasai; Shu Yamaguchi
Original assignee: Kao Corporation
Priority date: 2003-05-15
Filing date: 2004-05-14
Publication date: 2004-11-25
Also published as: MY140125A; WO2004101721A3; EP1624049A2; CN1774496A; CN1774496B; EP1624049A4

Abstract

A sliding property improver for use in washing which comprises potassium metaphosphate; a detergent composition comprising said sliding property improver for use in washing and a solubilizing agent; a method of washing by hand which comprises carrying out under a condition wherein a concentration of potassium metaphosphate is 30 mg/L or more and a liquor-goods ratio is 2 or more; a sliding property improver granule for use in washing which comprises potassium metaphosphate; and a detergent composition comprising said sliding property improver granules for use in washing and a solubilizing agent. The above sliding property improver for use in washing and the sliding property improver granule for use in washing are suitably used also in washing clothes or the like by hand, in particular, that involving immersion for a long time.

Description

Description Sliding property improver for laundry Technical field to which the invention pertains

The present invention relates to a laundry slipperiness improving agent for avoiding damage to cloth, and a laundry slipperiness improving agent granule. Specifically, by improving the smoothness between the items to be washed during hand-washing, it is possible to improve the hand-washing properties, such as being able to wash with light force and increasing the speed of rubbing the laundry (the number of rubs per hour). Also, the present invention relates to an additive for washing based on a completely new concept for suppressing damage to the object to be washed due to friction between the objects to be washed and hand cuts and abrasions caused by rubbing of the hand with the object to be washed. The present invention also relates to a detergent composition containing the slipperiness improver and the granulate. Furthermore, the present invention relates to a method for hand washing and washing in the presence of potassium metaphosphate. Also, in washing machine washing, the present invention relates to a method for avoiding damage to fabric by improving slipperiness between fibers against damage to fibers caused by a mechanical force such as agitation and the like, resulting in loss of shape. Background art

There are two main types of washing methods: hand washing and washing machine washing. In recent years, washing machine washing has been increasing due to the spread of washing machines. However, there is still a lot of need for hand washing from the viewpoint of dirt removal and economy.

Therefore, a detergent having favorable physical properties during hand washing has been developed. For example, as described in Japanese Patent Application Laid-Open No. 10-504556, hand washing is performed by blending anionic surfactant, cationic surfactant, and nonionic surfactant in a specific ratio. A method for improving skin irritation during washing is disclosed. In addition, regarding foam control, generally high foaming surfactants such as LAS and AS are used for increasing foam, nonionic surfactants such as polyoxyethylene alkyl ether are used for foam control, It is known that stones or the like are used to improve the foam-removing property during rinsing. More specifically, the solubility and crystallization of the anion surfactant, the specific nonionic surfactant, and the fatty acid stone in a specific ratio are disclosed in Japanese Patent Publication No. 8-13987. A detergent composition having excellent foaming and rinsing properties is disclosed.

However, there has been no study focused on a technique for improving ease of hand washing (slipperiness when rubbing an object to be washed). SUMMARY OF THE INVENTION

[1] A laundry slipperiness improver containing potassium metaphosphate,

(2) The slipperiness improving agent for hand-washing laundry according to the above (1), wherein the KZP molar ratio of potassium metaphosphate is less than 1.

(3) the hand-washing slipperiness improver according to the above (1) or (2), which is for hand-washing,

(4) a detergent composition comprising the laundry slipperiness improver according to the above (1) and a solubilizing agent,

[5] the detergent composition according to the above [4], wherein the amount of the solubilizing agent contains at least one equivalent of the replacement ion source relative to the lithium ion in the potassium phosphate solution;

(6) the detergent composition according to (4), further comprising a surfactant and / or a builder;

[7] The detergent composition according to the above [6], wherein the builder comprises 5% by weight or more of a sequestering agent having a calcium ion capturing ability of 100 mg Ca C〇 ₃ Zg or more; The detergent composition according to the above (7), wherein the blocking agent is a water-soluble organic substance, (9) the detergent composition according to the above (4), further containing a silicate.

(10) the detergent composition according to (9), wherein the silicate is sodium silicate; (11) the detergent composition according to (4), further comprising a phosphate; (12) the detergent composition according to (11), wherein the phosphate is sodium tripolyphosphate;

(13) Washing hands and washing under the condition of potassium metaphosphate concentration in water of 3 OmgZL or more and bath ratio of 2 or more,

(14) a laundry slipperiness improver granule containing potassium metaphosphate,

[15] The laundry slipperiness improver granule according to the above [14], wherein the average particle size of the potassium metaphosphate is 0.5 m or more and 200 im or less.

(16) The washing slipperiness improving agent granule according to the above (14), which is used for hand washing and washing; (17) the washing slipperiness improving agent according to the above (14), further comprising a binder substance,

[18] the abrasion improving agent granule for washing according to [17], wherein the binder substance is polyethylene glycol;

(19) The above-mentioned (14), wherein the average particle size is 100 / m or more and less than 2000 m.

(20) The laundry slipperiness improver granule according to the above (14), further comprising a solubilizing agent.

[21] a detergent composition comprising the granulated laundry slipperiness improver according to [14] and a solubilizer;

(22) a detergent composition containing the granulated granular material for washing smoothness according to (20), (23) the amount of the solubilizing agent is at least 0.5 equivalent to the potassium ion in potassium metaphosphate; The detergent composition according to the above (21), and

[24] The detergent composition according to the above [21], further comprising a surfactant and / or a builder.

About. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram showing a calibration curve created in a Ca ion trapping ability measurement method using a calcium ion electrode, showing the relationship between the logarithm of calcium ion concentration and the potential,

FIG. 2 is a schematic diagram showing the relationship between the concentration of calcium ions produced in the method for measuring Ca ion trapping ability using a calcium ion electrode and the amount of sample dropped. The calcium ion concentration at the sample drop amount A in FIG. 2 is the calcium ion trapping ability of the sample. DETAILED DESCRIPTION OF THE INVENTION

The present invention is intended to improve the smoothness between objects to be washed at the time of hand-washing, so that the laundry can be washed with a light force and the speed of rubbing the laundry (the number of rubs per hour) is easily increased. It facilitates hand-washing, and also provides a hand-care effect in which the skin after drying by hand-washing is soft and smooth, and a clothing-care effect that avoids mold collapse caused by mechanical forces such as agitation in washing machine washing. Washability improving agent for washing, slipperiness improving agent for hand washing, detergent composition containing these smoothing improver, and slipperiness when rubbing objects to be washed during hand washing. The present invention relates to an improved hand washing method.

In addition, before hand-washing, in many cases, the object to be washed is immersed in a solution in which the detergent composition is dissolved in water for several minutes to several hours, and then left to stand. On the other hand, the effect of improving slipperiness exhibited by dissolution of potassium metaphosphate decreases with time. By increasing the particle size of the potassium metaphosphate powder, it is possible to extend the duration of the slipperiness, but unresolved potassium metaphosphate and adhesion to clothing become problems. Therefore, the present invention can improve the smoothness between the objects to be cleaned both when not immersed and when immersed without causing undissolved potassium metaphosphate and adherence to clothing. Granulated material for improving the smoothness for washing, which can be easily washed by hand washing because it is maintained and can be washed with a light force and the speed of rubbing the laundry (the number of times of rubbing per hour) is increased. The present invention relates to a detergent composition containing a granulated agent.

These and other advantages of the present invention will become apparent from the description below. In response to the need for easy hand-washing, the present inventors have conducted intensive studies focusing on completely new physical properties, namely, slipperiness when rubbing objects to be washed together during washing. A washing slipperiness improver containing potassium phosphate is added separately from the detergent composition at the time of hand washing and washing, or a detergent composition containing the above-mentioned washing slipperiness improver is used. The above problems have been solved, and the present invention has been completed. Furthermore, taking into account that in many cases hand washing and washing are started after immersion washing for several minutes to several hours, potassium phosphate alone is granulated alone, or a binder and / or other materials. By using the ingredients and granulated material, not only during hand washing and washing immediately after addition but also in hand washing after immersion washing for several minutes to several hours, washing with light force and speed of rubbing the laundry ( It has been found that the number of rubs per hour increases, and that the feeling of hand washing is enhanced, and the present invention has been completed.

The slipperiness improver for washing can be used as a detergent containing a slipperiness improver by mixing it with a detergent, or can be used directly at the time of washing and added separately from the detergent.

The laundry slipperiness improver of the present invention comprises potassium mesylate, and specifically refers to potassium metaphosphate alone or a mixture of potassium metaphosphate and another base.

Potassium metaphosphate will be described later. In addition, other bases can be used as long as they are generally used as a detergent composition without inhibiting the function of potassium metaphosphate. For example, sodium sulfate, zeolite, polyethylene glycol, alkyl sulfate, or the like can be used as appropriate.

The amount of potassium metaphosphate is preferably from 30 to 100% by weight, more preferably from 50 to 100% by weight, in the laundry slipperiness improver.

When the laundry slipperiness improver having such a configuration is potassium metaphosphate alone, potassium metaphosphate may be used as it is, or may be pulverized into a fine powder.

In the case of a mixture of potassium metaphosphate and another base, it can be produced by mixing these components by a known method.

INDUSTRIAL APPLICABILITY The laundry slipperiness improver of the present invention improves the slipperiness between objects to be washed during hand-washing, thereby facilitating hand-washing, further enhancing the feel in hand-washing, and further improving hand care and clothing care. It has the action of: Therefore, the present invention also relates to a slipperiness improving agent for hand washing and washing.

The form of the slipperiness improver for washing (hereinafter abbreviated as "slipperiness improver") is not particularly limited, and may be in any form of powder, granules, liquid, or slurry / paste. Is preferably used in the form of powder or granules in order to quickly and uniformly express the same in clothing.

In addition, when the slipperiness improver is formed into granules or capsules, the potassium diphosphate is not left undissolved or adheres to clothing. In both cases, it is said that the improved smoothness between the objects to be washed is maintained, and that the washing with light force and the speed of rubbing the laundry (the number of rubbing per hour) are increased, so that the user can easily wash by hand. There are advantages. Such a granulated laundry slipperiness improver will be described later.

The slipperiness improver or the slipperiness improver granule of the present invention is preferably contained in a detergent composition from the viewpoint of simplicity and solubility during use. Note that the slipperiness improver is not limited by the composition and form of the detergent composition to be used and the production method and the like. The effect can be exhibited in all detergent compositions containing the above-mentioned solubilizer. Detergent composition>

The detergent composition of the present invention has one major feature in that the detergent composition contains the slipperiness improver and the no-slipperiness improver granules and a solubilizer. Due to such a characteristic, the washing liquid in which the detergent composition is dissolved during washing becomes a lotion-like viscous solution, and even during hand washing and washing, the smoothness between the articles to be washed is improved, so that a light force is applied. Improves hand washability, such as being able to wash and increasing the speed of rubbing laundry, and has a hand-care effect and clothing care effect that makes the skin feel softer and smoother after drying after hand-washing. You.

The detergent composition may be in any form, such as powder, granule, liquid, or paste, and may be formed into agglomerates, tablets, etc. by secondary processing. It is preferably in the form of a powder or granules.

In the present invention, the washing liquid refers to a liquid for performing washing, such as a state in which the detergent composition is dissolved and suspended. Hereinafter, each component used in the present invention will be described.

1. Potassium metaphosphate

The potassium phosphate of the present invention used in the present invention has a very low solubility in water, but a salt with a solubilizer (a compound containing a sodium ion source, a lithium ion source, and an ammonium ion source) in a washing liquid. It is a substance that exhibits water solubility upon exchange. Even (KP 0 ₃₎ high molecular weight potassium metaphosphate represented by eta (molecular weight = about 10,000 to several tens of million) is to improve the sliding property between the washing净物during hand-washing among the hand-washing property It is suitable for improving. Here, the potassium metaphosphate includes those in which potassium is partially replaced by sodium lithium or the like. Potassium metaphosphate is generally produced by the following method.

nKH ₂ P〇4 → (ΚΡ〇 ₃ ) η + ηΗ ₂ 〇

That is, by the arc heating the potassium dihydrogen phosphate (ΚΗ ₂ Ρ0 ₄₎ performing intermolecular dehydration, but potassium metaphosphate is produced, the I Ri various degree of polymerization factor of the difference, such as heating temperature and time The product is obtained, and the higher the temperature of the dehydration reaction, the greater the degree of polymerization. From the viewpoint of slipperiness after immersion, the firing temperature for performing the dehydration reaction is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more. Ot: preferably not more than 1,300 or less, more preferably not more than 1200. .

The molecular weight of potassium metaphosphate is preferably 10,000 or more, more preferably 100,000 or more, still more preferably 200,000 or more, and still more preferably 500,000 or more, from the viewpoint of improving hand-washing properties. From the standpoint of availability, the amount is preferably 50,000,000 or less, more preferably 20,000,000 or less. In addition, potassium metaphosphate has no particular upper limit in molecular weight as long as it exhibits water solubility in the presence of a solubilizing agent, and the higher the molecular weight, the higher the effect of improving hand washability. In addition, even when a part of sodium dihydrogen phosphate or the like is contained in addition to the dihydrogen phosphate phosphate at the time of heating, the effect as a slipperiness improving agent can be exhibited as long as it is subjected to intermolecular dehydration (condensation).

From the viewpoint of slipperiness after immersion, potassium metaphosphate preferably has a KZP molar ratio of less than 1, more preferably (excluding 1) to 0.8, more preferably 0.8. It is preferably from 999 to 0.9, more preferably from 0.999 to 0.94, more preferably from 0.995 to 0.96, more preferably from 0.99 to 0.98. The K / P molar ratio in the present invention refers to a value measured by a measuring method described in Examples described later.

The content of potassium phosphate in the detergent composition is preferably 0.5 part by weight or more, more preferably 1 part by weight or more, and more preferably 3 parts by weight with respect to 100 parts by weight of the detergent composition, from the viewpoint of improving the hand washing ability. More preferably, more preferably 5 parts by weight or more, 7 It is more preferably at least 10 parts by weight, more preferably at least 10 parts by weight. In addition, from the viewpoint of maintaining the handleability of the object to be washed after washing, the amount 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.

In addition, it is preferable that the compounding amount of potassium phosphate is also increased in accordance with the amount of the nonionic surfactant in the detergent composition and the ratio of the nonionic surfactant to the total surfactant components. In addition, from the viewpoint of obtaining good hand washability, the concentration of potassium metaphosphate in water when the detergent composition is dissolved to prepare a washing liquid is preferably 15 mg / L or more.

OmgZL or more is more preferable, and 6 OmgZL or more is still more preferable. Further, from the viewpoint of the handling of the object to be cleaned after cleaning, it is preferably 300 OmgZL or less.

OmgZL or less is more preferred, and 100 OmgZL or less is even more preferred. Furthermore, the bath ratio (the ratio of the weight of water to clothing: the weight of water and the weight of clothing) is reduced, the hardness of the washing liquid is increased, the amount of nonionic surfactant in the detergent composition and the ratio to the total surfactant component are increased. It is preferable to increase the concentration of the potassium metaphosphate in water as the temperature rises.

2. Solubilizer

Potassium metaphosphate is extremely poorly soluble in water, but exhibits 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 a lithium or lithium ion source and / or an ammonium ion source capable of replacing potassium in potassium metaphosphate. Therefore, in the detergent composition, the detergent composition is dissolved in water by using the slipperiness improving agent or the slipperiness improving agent granules containing potassium phosphate in combination with a solubilizing agent. Even when the washing is performed, potassium mesophosphate is dissolved, and the washing water becomes a lotion-like viscous solution. As a result, there is an advantage that the smoothness between the objects to be washed is improved and the hand washing is improved.

The solubilizing agent includes any sodium source and Z or lithium ion source and / or ammonium ion source that replace potassium in potassium phosphate. More useful are the inorganic salts of sodium, lithium and ammonium, and Machine salts, for example, sodium carboxylate such as sodium carbonate, sodium chloride, sodium sulfate, sodium sulfite, sodium citrate, sodium phosphate, sodium silicate, polysodium polycarboxylate, monosodium polysulfonate , Lithium halides and lithium sulfate. Among them, inorganic or organic salts of sodium are most preferred. Surfactants, salt forms of fatty acids, sequestering agents, and the like can also be solubilizing agents.

The potassium metaphosphate exhibits water solubility by replacing potassium ions in potassium metaphosphate with sodium ions and / or lithium ions and Z or ammonium ions. It is required to use it in a state where lithium can be dissolved. The effect can be realized if part of potassium in potassium metaphosphate can be replaced.However, from the viewpoint of economy, an amount of sodium that can completely replace potassium rim ions in potassium phosphate in the washing liquid can be obtained. The amount of solubilizer is preferred. The amount of the solubilizing agent is 0.5 equivalent or more when the amount capable of supplying the same amount of sodium ion and / or lithium ion and / or ammonium ion as the potassium ion in the metaphosphoric acid sodium is 1 equivalent. It is preferably at least 1 equivalent, more preferably at least 2 equivalents, even more preferably at least 3 equivalents. On the other hand, in the presence of excess sodium ion and / or lithium ion and / or ammonium ion with respect to potassium ion, the effect of improving hand-washability is small. In this respect, the amount of the solubilizing agent is preferably equal to or less than 400 equivalents, more preferably equal to or less than 200 equivalents, and still more preferably equal to or less than 100 equivalents. In addition, from the viewpoint of maintaining the effect of improving slipperiness, the amount is preferably equal to or less than 30 equivalents, and more preferably equal to or less than 20 equivalents.

When the detergent composition contains necessary amounts of sodium ion and Z or lithium ion and / or ammonium ion for another purpose, it is not necessary to separately add a solubilizing agent. 3. Surfactants and / or builders

The detergent composition of the present invention can contain a surfactant and a Z builder. As the surfactant, those generally used can be used. Examples include anionic surfactants and nonionic surfactants. Examples thereof include alkyl benzene sulfonate, alkyl ether or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, alkane sulfonate, ァ -acyl amino acid type surfactant, Alkyl or alkenyl ether carboxylate, amino acid surfactant, anionic surfactant such as alkyl or alkenyl phosphate or a salt thereof, polyoxyalkylene alkyl (or alkenyl) ether, polyoxyethylene alkyl phenyl ether, Nonionic surfactants such as higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, and fatty acid glycerin monoesters.

Among them, from the viewpoint of enhancing the sliding effect, alkyl benzene sulfonates, alkyl ether sulfates, and alkyl sulfates are preferred, and sodium alkylbenzene sulfonate is more preferred.

The content of the anionic surfactant and the nonionic surfactant is preferably 5% by weight or more, more preferably 10% by weight or more, from the viewpoint of cleaning performance in the detergent composition. % By weight or more, more preferably 15% by weight or more, even more preferably 17% by weight or more. From the viewpoint of powder properties, the content is preferably 40% by weight or less, more preferably 35% by weight or less, still more preferably 30% by weight or less, and even more preferably 26% by weight or less.

In the detergent composition of the present invention, a surfactant such as a benzoin-type amphoteric surfactant, a phosphate ester-based surfactant, limestone, or a cationic surfactant can be appropriately compounded. Examples of the builder include a sequestering agent, an alkali agent, and a recontamination inhibitor.

Above all, as the amount of hardness components in the wash water increases, the effect of improving the slipperiness decreases.Therefore, as a builder, a sequestering agent is added to the detergent composition to capture the hardness components in the wash water. Is very effective in expressing the performance of potassium phosphate. Further, a metal ion sequestering agent having a calcium ion trapping ability of at least 10 Omg CaCOaZg is more effective. Examples of such sequestering agents include ion exchangers such as zeolite and crystalline gaylate, polymers such as polyacrylate, acrylic acid-maleic acid copolymer (salt), sodium tripolyphosphate, ethylenediamine Examples include water-soluble organic substances such as chelating agents such as tetraacetate, methylglycine diacetate and citrate.

Sodium carbonate and amorphous sodium gayate are not included in the sequestering agent. Examples of the alkaline agent include a carbonate and a silicate. From the viewpoint of enhancing the sliding effect, amorphous sodium gateate is preferred.

Examples of the anti-redeposition agent include carboxymethyl cellulose, polyethylene glycol and the like.

The amount of the builder is preferably not less than 5% by weight, more preferably not less than 10% by weight, still more preferably not less than 15% by weight, more preferably not less than 20% by weight, in the detergent composition, from the viewpoint of improving the hand washability. %, More preferably 60% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, from the viewpoint of the balance of the composition.

4. Gayates and phosphates (excluding potassium metaphosphate)

The detergent composition of the present invention has an advantage that the slipperiness improving effect can be further improved by blending a gay salt and a phosphate.

Amorphous and crystalline ones are known as the maleic acid salt. Can be. Here S i 0 _₂ / M ₂ O ratio (M is an alkali metal) 1 or more on a, preferably 1. 5 or more, more preferably 2 or more, preferably 4 or less, 3 or less is more preferable. Here, amorphous sodium silicate is more preferable, and JIS No. 1 sodium silicate and JIS No. 2 sodium silicate can be suitably used. The amount is preferably 3% by weight or more, more preferably 5% by weight or more, and even more preferably 7% by weight or more in the detergent composition from the viewpoint of hand-washability. In addition, from the viewpoint of suppressing the undissolved portion at the time of washing while maintaining a high smoothness improving effect, the amount is preferably 30% by weight or less, more preferably 20% by weight or less.

Examples of the phosphate include sodium tripolyphosphate, sodium pyrophosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, etc., and sodium triribophosphate is preferred. Therefore, in the detergent composition, the content is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more. In addition, from the viewpoint of achieving both the smoothness improving effect and the detergency, it is preferably at most 40% by weight, more preferably at most 30% by weight.

In the present invention, of the above components, the sequestering agent, the silicate, and the phosphate are blended in the above amounts, so that even if the blending amount of potassium phosphate is reduced, hand washing and washing properties are improved. There is a merit that can be kept well.

5. Other additives

In the detergent composition of the present invention, an enzyme, a fragrance, a fluorescent dye, a pigment, and the like can be appropriately blended.

6. Method for producing detergent composition

The detergent composition of the present invention having the above-described configuration can be produced by appropriately mixing the above components with a known method. As described above, the potassium metaphosphate contained in the detergent composition of the present invention becomes water-soluble in water in the presence of a solubilizing agent, as described above. Is preferably reduced. For example, when a detergent composition is produced by a spray drying method, a slipperiness improving agent and / or a granulated material having a slipperiness improving agent in a granulation step, a surface modification step, an after blending step, etc. after the spray drying step. Is desirably added.

Also, when a detergent composition comprising components other than the slipperiness improver at the time of hand-washing and a slipperiness improver are separately added to prepare a washing liquid, in order to suppress generation of sprinkling during dissolution, As the laundry slipperiness improver, it is preferable to use a mixture of potassium phosphate and another base.

Further, the solubilizer may be contained in the laundry slipperiness improver or the slipperiness improver granule and / or in the detergent composition, and need not necessarily be contained in the detergent composition.

Examples of such detergent compositions include, for example, the compositions described in Patent Office Publication 10 (1998) and 25 (7159) Well-known conventional technology collection (powder detergent for clothing), and detergent compositions obtained by the production method. .

The granulated laundry slipperiness improver of the present invention is characterized by containing potassium metaphosphate and being a granulated product.

The granulated laundry slipperiness improver of the present invention having such a characteristic can be used for a long time if not soaked without causing unmelted potassium phosphate to adhere to clothes. Even in this case, good smoothness between the objects to be washed can be maintained, and it is possible to easily wash by hand, such as being able to wash with a light force and increasing the speed of rubbing the laundry.

In the case of washing machine washing, the cause of mold collapse caused by mechanical force such as stirring. The damage to the fabric can be avoided by increasing the smoothness between the fibers against the damage of the fiber.

Therefore, the present invention also relates to a granulation of a slipperiness improver for hand washing and washing.

In the present invention, the granulated product refers to a product obtained by granulating potassium metaphosphate alone or a product obtained by granulating potassium metaphosphate and a binder material and Z or other components. Capsules and the like can be mentioned.

According to the present invention, the granulation as described above improves the handleability at the time of addition to the detergent composition in the production process and suppresses the generation of flour when added separately from the detergent composition at the time of washing. There is also the advantage that it can be done.

Hereinafter, each component used for the granulated product of the laundry slipperiness improving agent of the present invention (hereinafter, also simply referred to as a granulated product) will be described.

1. Potassium metaphosphate (when used for granules)

The potassium mesophosphate may be the same as that used in the slipperiness improver.

From the viewpoint of handling, the average particle size of potassium phosphate mixed with the granulated product is preferably 0.5 im or more, more preferably 1 / m or more, still more preferably 5 m or more, and 10 // m or more, more preferably 30 m or more. On the other hand, from the viewpoint of granulation properties and solubility (suppression of adhesion to residual clothing), it is preferably at most 300 / m, more preferably at most 200 zm, even more preferably at most 100 m. . Examples of a method for adjusting the average particle size of potassium metaphosphate to the above range include a method of pulverizing with a known pulverizer such as an atomizer manufactured by Fuji Baudal Co., Ltd. and a pin mill manufactured by Hosokawa Micron Corporation.

By thus reducing the particle size of potassium mesophosphate used for granulation, there is an advantage that unmelted residue and adhesion to clothing can be suppressed.

The content of potassium metaphosphate in the granules is 10% by weight from the viewpoint of mixability. And more preferably 30% by weight or more, more preferably 50% by weight or more. On the other hand, from the viewpoint of solubility, 95% by weight or less is more preferable, and 90% by weight or less is further preferable. , 80% by weight or less is more preferable.

In the present invention, the potassium metaphosphate may be granulated alone, or may be granulated by mixing with a binder substance and other components.

2. Binder substance

The binder substance is not particularly limited as long as it has an ability to bind components constituting the laundry slipperiness improver granule, but from the viewpoint of solubility of the granule, a water-soluble binder is used. From the viewpoint of storage stability, a thermoplastic water-soluble binder having a cohesion of 40 or less and having binding properties is more preferable. Examples of the water-soluble binder include polyethylene render alcohol having an average molecular weight of 2,000 to 30,000, preferably 5000 to 15,000, and saturated or unsaturated fatty acids having 8 to 18 carbon atoms, and polyethylene glycol is more preferable. These may be used alone or in combination. The amount of the binder substance is preferably 0.05 times or more, more preferably 0.07 times or more, more preferably 10 times or less, more preferably 4 times or less, and more preferably 4 times or less with respect to potassium metaphosphate. More preferably, the amount is twice or less.

3. Other ingredients

As the other components in the granulated material, any one which is generally used as a detergent composition without inhibiting the action of potassium phosphate may be used, and a solubilizing agent, a sequestering agent, Gay salts and phosphates can be used as appropriate. Among them, the granulated product has an advantage that it is not necessary to add a solubilizing agent to the detergent body by containing the solubilizing agent. The solubilizer may be any of those described above.

4. Manufacturing method of granulated material The method for producing the granulated product of the present invention is not particularly limited. For example, the granulated product can be produced by a stirring tumbling granulation method, an extrusion granulation method, a spray cooling method, or the like. In the case of the stirring tumbling granulation method, for example, other components such as potassium metaphosphate, a binder substance and a solubilizing agent (a sodium source and / or a lithium source) are mixed, and the temperature is raised to dissolve the binder substance. A method of cooling after granulation, a method of adding a molten binder substance while stirring and mixing other components such as potassium metaphosphate, and a solubilizing agent (a sodium source and / or a lithium source), and granulating, While stirring and mixing other components such as potassium acid and a solubilizing agent (a sodium source and a Z or lithium source), an aqueous binder solution is added, granulated, and then dried. In the case of the extrusion granulation method, for example, a method in which other components such as potassium metaphosphate, a binder substance, and a solubilizing agent (a sodium source and a lithium or lithium source) are melt-mixed, and granulated through an extrusion granulator; There is a method of melting and mixing other components such as potassium acid, aqueous binder solution and solubilizing agent (sodium source and / or lithium source), granulating through an extrusion granulator, and drying. In the case of the spray cooling method, for example, melt and mix other components such as meta-phosphoric acid, binder material and solubilizer (sodium source and / or lithium source), and spray from a nozzle into a low-temperature space to obtain granules. There are methods.

When a solubilizing agent is used, potassium metaphosphate is dissolved and thickened by water in the presence of the solubilizing agent, so that it is preferable to suppress moisture during granulation. In such a case, it is preferable to use a thermoplastic water-soluble binder having a binding property of 40 or less as a binder substance in the following. Examples of such a water-soluble binder include polyethylene glycol having an average molecular weight of 2,000 to 30,000, preferably 5,000 to 15,000, and saturated or unsaturated fatty acids having 8 to 18 carbon atoms. Polyethylene blender is more preferred. Further, when water and a binder aqueous solution are used as the binder substance, it is preferable to sufficiently dry in a subsequent step.

As a device used for granulation, for example, Fukae Kogyo Co., Ltd. High-speed mixers, pro-share mixers manufactured by Taiheiyo Kikai Co., Ltd., and extrusion granulators include, for example, Fuji Padal Co., Ltd.'s Pellet Yuichi Double and Twin Dome Daran.

After granulation, the granulated product obtained by such a method may be subjected to crushing, spheronization and the like, if necessary, for the purpose of improving the appearance and the yield. Apparatuses used for crushing are Dalton Power Mill, Fuji Baudal Co., Ltd. Flash Mill, Fitzpatrick (USA) Fitz Mill, Comil (California) A speed mill manufactured by Seika Okada Co., Ltd., and the like, and a melomerizer manufactured by Fuji Baudal Co., Ltd. are exemplified as the sphering device. When the thermoplastic water-soluble binder is used, the temperature supplied to the crusher is preferably cooled to around room temperature.For example, the granulated material is supplied to a vibration cooler, and the granulated material is cooled to a predetermined temperature and then crushed. When crushed, there is an advantage that adhesion of the crushed material in the crusher is suppressed.

The sized granules may be adjusted to a desired particle size by classification in order to reduce fine powder and / or coarse powder. By classifying and adjusting the particle size, the appearance during use can be improved. The fine and coarse particles or coarse powder generated by the classification can be used, for example, by pulverizing and using as a raw material for granulation or by re-melting to improve the yield.

5. Quality of granulated material

As the particle size of the granulated product of the present invention, the average particle size is preferably 100 or more, more preferably 150 m or more, and still more preferably 200 ° or more, from the viewpoint of the sustainability of the effect of improving the washability. preferable. Further, from the viewpoints of appearance and solubility, it is preferably less than 2000, more preferably less than 1500 zm, even more preferably less than 1000 m. Among them, a spherical shape is most preferable from the viewpoint of appearance and classification, and in the case of an extruded granulated material which does not perform spheroidization, a ratio of an extruded diameter to a length close to 1 is preferable. Also, from the viewpoint of appearance, it is preferable that the particle size distribution is as uniform as possible. New On the other hand, from the viewpoint of storage stability, the moisture value in the granulated product is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less in the final product. The granulated slipperiness improver produced by such a method can be contained in the detergent composition in the same manner as the slipperiness improver described above. By using the slipperiness improving agent and / or the slipperiness improving agent of the present invention having the above-mentioned constitution, the detergent composition containing granules can be pickled without causing undissolved potassium metaphosphate and adherence to clothing. In both cases, when not laid, and when immersed, the improvement of the smoothness between the objects to be cleaned is maintained, and the effect of facilitating hand washing and washing without impairing the cleaning property and also enabling the hand care is realized. Is done.

The hand-washing method of the present invention is a method in which washing is performed by hand-washing under the conditions of a concentration of potassium metaphosphate in water of 3 O mg / L or more and a bath ratio of 2 or more.For example, potassium metaphosphate is part of a detergent component. Or by adding it to the washing liquid separately from the detergent component and then washing by hand. As a specific embodiment, there is a method in which the slipperiness improver or the slipperiness improver granulate is added to a washing liquid as a part of the detergent component or separately from the detergent component, and washing is performed by hand washing.

In the present invention, as described above, by adjusting the concentration of potassium metaphosphate in water and the bath ratio to specific ranges, the washing liquid becomes a lotion-like viscous solution, and the smoothness between the objects to be cleaned is improved. Also, with the increase in the bath ratio, the solubility of potassium metaphosphate and the adsorption on the surface of the object to be cleaned are promoted, and the feeling that the smoothness between the objects to be cleaned is improved is obtained. is there.

The concentration of potassium metaphosphate in water is preferably 15 mg / L or more, more preferably 30 mg ZL or more, and further preferably 60 mg ZL or more, from the viewpoint of improving slipperiness. Preferred. In addition, from the viewpoint of handleability of the article to be washed after washing, it is preferably at most 300 mg ZL, more preferably at most 150 mg ZL, even more preferably at most 100 mg / L. In addition, the concentration of potassium phosphate water in water increases as the bath ratio decreases, the washing water hardness increases, the amount of nonionic surfactant in the detergent composition and the ratio to the total surfactant components increase. Preferably.

The bath ratio (the ratio of the weight of water to clothing) is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and more preferably 5 or more, from the viewpoints of solubility and adsorption between the objects to be washed. More preferred. In addition, from the viewpoint of ease of washing, it is preferably 20 or less, more preferably 15 or less. By using the washing method of the present invention having the above-described configuration, it is possible to improve the slipperiness when rubbing the objects to be washed at the time of hand washing, in addition to being able to wash with a light force and By increasing the speed of rubbing (the number of rubs per hour), the feeling of hand washing is enhanced, and the effect that hand care is also achieved is exhibited.

In addition, by using the washing method of the present invention, not only hand washing but also washing machine washing can improve the slipperiness between the fibers against damage to the fibers caused by mold deformation caused by mechanical force such as stirring. Thus, a so-called clothing care effect that cloth damage can be avoided can be exhibited.

Also, without causing the undissolved potassium metaphosphate and sticking to clothing, the improvement of the smoothness between the objects to be cleaned is maintained, regardless of whether it is not immersed or immersed. By increasing the speed with which laundry can be rubbed and the speed with which the laundry is rubbed (the number of rubs per hour), the feeling of hand washing can be enhanced, and the effect that hand care can also be achieved. In the present invention, hand-washing is performed under washing conditions according to the following hand-washing evaluation method. By performing rinsing, it is possible to evaluate a more preferable slipperiness improving effect. In addition, an increase in the viscosity of the washing liquid caused by the addition of potassium metaphosphate causes the appearance of nullness, and as a result, the slipperiness is improved. Therefore, the hand washing washability can be quantitatively evaluated by measuring the viscosity of the washing liquid.

[Hand washing conditions]

The method for evaluating hand washing in the present invention will be described below. 2 5 was adjusted to 8 9. 3 mg C a C_〇 ₃ 2 liters of hard water corresponding to Noritsutoru (C a ZM g molar ratio 7 Z 3) the diameter 3 O cm, depth 1 3 cm, volume 8.2 After filling into a polypropylene wash basin (YAZAKI) of L and weighing 15 g of the detergent composition into water, continue stirring by hand so that the water does not scatter from the wash basin. 30 seconds after the start of stirring, a 100% cotton T-shirt (Gunze white, L size) is soaked in the washing water in the wash basin so that the entire T-shirt is sufficiently wet, and then the back of the T-shirt Grip the chest of the T-shirt with both hands and rub the chest of the T-shirt together. At this time, the part to be rubbed is taken out of the washing water. After rubbing three to five times, immerse the rubbed part in washing water. The ease of rubbing when rubbing is judged as slipperiness, and ranks 1 to 5 ranks. When this evaluation is performed using only the above-mentioned adjusted water, the wrinkles of the T-shirt impede the smoothness, and since there is no bubble in the portion to be rubbed, it is extremely difficult to rub, and the smoothness is poor. At this time, the sliding property is set to 1. The status of each rank is shown below.

Rank 1: Very low slipperiness, squeaky feeling, and very difficult to wash by hand.

Rank 2: Low slipperiness, squeaky feeling, and difficult to wash and wash by hand.

Rank 3: Moderate smoothness, no washout and hand wash.

Rank 4: High slipperiness, no squeaky feeling, and hand-washing is easy. Rank 5: Extremely smooth, no squeaky feeling, and easy to wash by hand. In the above test, the average of the panelists' evaluation results of the six panelists was determined and ranked. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Table 1 shows the compositions of the detergent compositions obtained in the examples and comparative examples. Hereinafter, methods for measuring physical properties in the present invention will be described.

(Measurement of metal ion trapping ability)

The metal ion-capturing ability was measured by the following methods, respectively, when the sequestering agent was an ion exchanger and when the polymer was a chelating agent.

In case of ion exchanger>

Accurately weighed ion exchanger 0. lg, calcium chloride aqueous solution (concentration 500 p pm as a C AC_〇 ₃₎ was added during 10 Om l, was stirred for 60 minutes at 25, the hole size 0.2 Filtration was performed using a / zm membrane filter 1 (manufactured by Advantech, nitrocellulose), and the amount of Ca contained in 10 ml of the filtrate was measured by EDTA titration. From these values, the calcium ion exchange capacity (force exchange capacity) of the ion exchanger was determined.

All solutions were prepared using the following buffers.

Buffer; 0.1 M-NH ₄ C 1 -NH ₄ OH buffer (pH 10.0)

(1) Creating a calibration curve

A standard calcium ion solution was prepared, and a calibration curve showing the relationship between the logarithm of calcium ion concentration and the potential as shown in FIG. 1 was prepared. (2) Measurement of the ability to capture calcium ions

Approximately 0.1 lg of sample was weighed into a 10 OmL volumetric flask and brought to 10 OmL with the above buffer. To this was added dropwise C a C 12 aqueous solution, corresponding to 20000 p pm (C a C0 ₃ conversion) a (pH 1 0. 0) from Byuretsu Bok (blank was also measured).

Dropping was carried out by adding portions C a C 1 ₂ aqueous 0. 1 to 0. 2m 1, reads the voltage at that time was determined calcium ion concentration from the calibration curve of Figure 1.

The calcium ion concentration at the sample dropping amount A in FIG. 2 became the sample's ability to capture calcium ions.

The molecular weight of potassium metaphosphate refers to the weight-average molecular weight, which was measured using gel permeation chromatography (GPC) under the following conditions, and converted using a calibration curve of polyethylene render recall.

Column: GMPWXL + GMPWXL manufactured by Tosoh Corporation

Mobile phase; 0.02M phosphate buffer acetonitrile = 90 10 (weight ratio) Temperature: 40 ° C

Flow rate: 1 mL / min

Sample concentration and amount; 0.1% by weight (Solubilizer sodium tripolyphosphate 0.6% by weight), 100 1

Detector: Differential Refractive Index Detector (R I D) Measurement method of average particle size of potassium metaphosphate>

Using a laser scattering particle size distribution analyzer (LA-920, Horiba, Ltd.), using a sample of ion-exchanged water at 25 under the conditions of a refractive index of 1.2, ultrasonic intensity of 7, ultrasonic irradiation time of 1 minute and stirring speed of 4 (Potassium metaphosphate) is measured and the metaphosphoric acid power The average particle size (m) of the lithium was determined. The average particle size here refers to a median size.

Time for measuring pickling time>

Detergent composition containing a slipperiness improver for laundry or detergent composition containing a granulated material for slipperiness improver for laundry was adjusted to 25: 89.3 mgCaCO3 50 Oml of hard water equivalent to ₃ liters of hard water (C & 1 ^ 8 molar ratio 7 / ^/ 3), stirred with a stirrer piece (7 mm X 4 Omm) for 1 minute (700 rZm), stopped stirring, and allowed to stand for 10 minutes. After standing, stirring (300 r / m) was started again, and at the same time, the viscosity was measured using an SV type viscometer (model number: SV-10, A & D Corporation). In a similar manner, the standing time was set from 20 minutes to 180 minutes in increments of 10 minutes. When the viscosity value after the start of re-mixing was 2 mP's or more, it was judged that the effect of improving the hand-washing property was improved by improving the slipperiness, and the maximum standing time at which the effect was improved was taken as the soaking time.

Dissolution residue evaluation method>

• Washing machine: Matsushita Electric "NA_F 42 Y5J

• Washing clothes: Black cloth [Blended (polyester / cotton = 65 35) weight ratio] 20 sheets' Detergent: 40 g

'Washing course: Medium water level (Water volume 40 liters) Washing 9 minutes-Rinse 2 times → Dehydration 3 minutes → Drying (Leave at 20, 40% RH for 24 hours) After drying clothes, 1 out of 20 black cloths

0 sheets were arbitrarily selected. At this time, adhesion of water-insoluble matter to the black cloth and persistence were evaluated as follows.

(Adhesion to black cloth, persistence)

No problem (no deposits) (〇)

There is some adhesion (△)

With deposit (X) Fabric care (MA test cloth) with large amounts of adhered residue (XX)>

(1) Pretreatment cloth adjustment

A fully automatic washing machine (Toshiba, AW-D802VP) was prepared, the amount of washing water was set to 45 L, and a total of 10 cotton T-shirts (about 2.2 kg) were put in this. In addition, a compact powder detergent (Attack, Kao Corporation) was added according to the standard usage amount, and washing was performed for 8 minutes, dehydration was performed for 3 minutes, rinsing was performed twice, dehydration was performed for 3 minutes, and dried in a dryer. This washing cycle was repeated five times to obtain a pre-treated cloth.

(2) Fabric care test (MA test cloth)

A test cloth (MAChineAction) manufactured by Tesfafabrics, Inc. was sewn to a part of five breasts of the T-shirt of the pretreated cloth with a sewing machine. The MA test cloth was described in FranntsSzarans; "Themechanianicaalactioni inwashying gmachinin s.

Prepare a fully automatic washing machine (Toshiba, AW-D802VP), set the amount of washing water to 45L, and weigh a total of 10 cotton T-shirts (about 2.2 kg) including the T-shirt sewn with the MA test cloth. I put it. Put 60g of detergent composition into the washing machine, wash 8 minutes, dehydrate 3 minutes, rinse twice, and dehydrate 6 minutes, remove the MA test cloth from the T-shirt without drying, and fray it The number of yarns was measured.

(3) Evaluation criteria for fabric care evaluation

For the judgment, the average value of the frayed threads of the five MA test cloths was obtained. Washing liquid feel> In the examples, the feel of the washing liquid was determined by checking the viscosity of the washing liquid by scrubbing the washing liquid up to a height of about 30 cm from the basin with the palm of the hand and then dropping the washing liquid into the basin. did.

After drying, the skin feel is as follows: After washing the hands for about 5 minutes, wash the washing liquid from the hands with tap water for 15 seconds, and turn the hands on the towel (100% cotton). The hand was allowed to stand for 10 seconds, and after absorbing the moisture on the front and back of the hand into the evening water, the feel of the hand was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕

A: The skin of the hand after drying is felt soft and smooth.

〇: No noticeable feeling after drying (same as when using detergent without potassium metaphosphate).

(Comparative Example 1)

Water 370 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40 wt% No. 2 silicate aqueous solution 50 kg, sodium carbonate 100 kg, sodium sulfate 147.5 kg, polyethylene glycol 5 kg, CBS type After mixing 2.5 kg of fluorescent dye and 125 kg of zeolite to prepare a homogeneous slurry, the slurry was spray-dried to obtain a detergent composition. Table 2 shows the slipperiness of the obtained detergent composition. Sliding property rank: Detergent composition of 2. The average value of the frayed threads of the five MA test cloths was 60 pieces.

(Comparative Example 2)

According to Example 3 described in Patent No. 323757, 465 kg of water, 48 kg of a 50% by weight aqueous solution of sodium dodecylbenzenesulfonate, 135 kg of an aqueous solution of 40% by weight of sodium polyacrylate, 120 kg of sodium carbonate , 60 kg of sodium sulfate, 9 kg of sodium sulfite, 83-type fluorescent dye 3, Zeola 300 kg were mixed to obtain a homogeneous slurry. This slurry was spray-dried to obtain base granules.

A mixture of 100 parts by weight of the base granules, 15 parts by weight of a nonionic surfactant, 15 parts by weight of an anionic surfactant and 1 part by weight of polyethylene dalicol is stirred and mixed to obtain a detergent composition. Was. Table 2 shows the slipperiness of the obtained detergent composition. Sliding property rank: Detergent composition of 1. The average value of the frayed yarn of the five MA test cloths was 60 pieces.

(Example 1)

4.0 kg of the detergent composition obtained in Comparative Example 1 was put into a concrete mixer (manufactured by Koyo Kikai Sangyo Co., Ltd., capacity: 40 L), followed by potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.). : 169-07045,? Mol ratio = 0.94) was added in an amount of 0.04 kg, and mixed at a tilt angle of 30 ° and a rotation speed of 2 Or / m for 3 minutes to obtain a detergent composition containing a slipperiness improving agent for washing. Obtained. Table 2 shows the slipperiness of the obtained detergent composition containing the slipperiness improving agent for washing. Slipperiness rank: 3 The skin feel after drying was very good. This was a detergent composition containing a slipperiness improver for washing.

(Example 2)

4. Deposit 4. kg of the detergent composition obtained in Comparative Example 1 into a concrete mixer (manufactured by Koyo Kikai Sangyo Co., Ltd., capacity: 40 L), and then add potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) : 169-07045) was added thereto and mixed at an inclination angle of 30 ° and a rotation speed of 2 Or / m for 3 minutes to obtain a detergent composition containing a slipperiness improving agent for washing. Table 2 shows the slipperiness of the obtained laundry detergent-containing detergent composition. Washing water in which this was dissolved turned into a viscous solution, and was a detergent composition containing a slipperiness improver for washing, with a very good skin feel after drying at a slipperiness rank: 5. (Example 3)

Water 377.5 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 140 kg, 40 wt% No.2 silicate aqueous solution 50 kg, sodium carbonate 100 kg, sodium sulfate 157.5 kg, polyethylene glycol 5 kg, C A homogeneous slurry is prepared by mixing 2.5 kg of BS dye, 125 kg of zeolite, 37.5 kg of a 40% by weight aqueous solution of sodium polyacrylate, and 5 kg of lipoxyl methylcellulose, and then spray drying the slurry. Then, 4.0 kg of the obtained detergent composition was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), and then potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045) Add 0.40 kg, 12 g of cellulase and 12 g of proteases, and mix for 3 minutes at a tilt angle of 30 ° and a rotation speed of 2 Or / m to perfume 12 g of fragrance. Obtained detergent composition containing . Table 2 shows the slipperiness of the obtained detergent composition containing the slipperiness improving agent for washing. The washing water in which this was dissolved turned into a viscous solution, and was a slippery rank: 5, a detergent composition containing a slipperiness improver for washing, having a very good skin feel after drying.

(Example 4)

347.5 kg of water, 200 kg of 50 wt% sodium dodecylbenzenesulfonate aqueous solution, 50 kg of 40 wt% aqueous solution of No. 2 silicate, 100 kg of sodium carbonate, 100 kg of sodium carbonate, 132.5 kg of sodium sulfate, 5 kg of polyethylene glycol, C A homogeneous slurry was prepared by mixing 2.5 kg of BS dye, 125 kg of zeolite, and 37.5 kg of a 40% by weight aqueous solution of acrylic acid-maleic acid copolymer, and then the slurry was spray-dried. 4. The resulting detergent composition 4. O kg was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), followed by potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045) ), And mixed at a tilt angle of 30 ° and a rotation speed of 2 Or / m for 3 minutes to obtain a detergent composition containing a slipperiness improver for washing. Got. Table 2 shows the slipperiness of the obtained laundry detergent-containing detergent composition. The washing water in which this was dissolved turned into a viscous solution, which was a slipperiness rank: 5 and was a detergent composition containing a slipperiness improver for washing, which had a very good skin feel after drying.

(Example 5)

Water 322.5 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 250 kg, 40 wt% No. 2 silicate solution 50 kg, sodium carbonate 100 kg, sodium sulfate 102.5 kg, polyethylene glycol 5 kg, C A homogeneous slurry is prepared by mixing 2.5 kg of BS dye, 125 kg of zeolite, 37.5 kg of 40% by weight acrylic acid-maleic acid copolymer aqueous solution and 5 kg of carboxymethyl cellulose, and then spraying the slurry After drying, 4.0 kg of the obtained detergent composition was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), and then potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) 169-07045), add 0.28 kg, 12 g of cellulase and 12 g of proteases, mix at 3 ° incline at 30 ° and 2 Or / m for 3 minutes, flavor with 12 g of fragrance, and wash. Detergent composition containing slipperiness improver I got something. Table 2 shows the slipperiness of the resulting detergent composition containing a slipperiness improver for washing. The washing water in which this was dissolved turned into a viscous solution, which was a slipperiness rank: 5 and was a detergent composition containing a slipperiness improver for washing which had a very good skin feel after drying.

(Example 6)

Water 370 kg, 50% by weight sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40% by weight aqueous solution of No. 2 silicate 50 kg, sodium carbonate 100 kg, sodium sulfate 130 kg, polyethylene glycol 5 kg, CBS dye 2.5 kg , 125 kg of zeolite and 17.5 kg of ethylenediaminetetraacetic acid were mixed to prepare a homogeneous slurry, and the slurry was spray-dried to obtain a detergent composition. 4.0 kg of the product was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), followed by 0.28 kg of potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045). The mixture was mixed for 3 minutes at a tilt angle of 30 ° and a rotation speed of 20 r / m to obtain a detergent composition containing a slipperiness improving agent for washing. Table 2 shows the slipperiness of the obtained detergent composition containing a washability improver for washing. The washing water in which this was dissolved turned into a viscous solution, which was a detergent composition containing a slipperiness improver for washing with a slipperiness rank of 5 and a very good skin feel after drying.

(Example 7)

Water 370 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40 wt% No. 2 silicate aqueous solution 50 kg, sodium carbonate 100 kg, sodium sulfate 135 kg, polyethylene glycol 5 kg, CBS dye 2. 5 kg, 125 kg of zeolite and 12.5 kg of methyldaricinine diacetate were mixed to prepare a homogeneous slurry, and the slurry was spray-dried. 4.0 kg of the resulting detergent composition was added to a concrete mixer (Koyo Machinery Industries, Ltd.). (Capacity: 40 L), 0.28 kg of potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045) was added, and the tilt angle was 30 ° and the rotation speed was 20 r. / m for 3 minutes to obtain a laundry detergent-containing detergent composition. Table 2 shows the slipperiness of the obtained detergent composition containing a washability improver for washing. The washing water in which this was dissolved turned into a viscous solution, which was a detergent composition containing a slipperiness improver for washing with a slipperiness rank of 5 and a very good skin feel after drying.

(Example 8)

Water 325 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40 wt% No. 2 silicate solution 125 kg, sodium carbonate 70 kg, sodium sulfate 147.5 kg, polyethylene glycol 5 kg, CBS After mixing 2.5 kg of dye and 125 kg of zeolite to prepare a homogeneous slurry, the slurry was spray-dried, and 4.0 kg of the obtained detergent composition was added to a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), and then add 0.28 kg of potassium metaphosphate (Wako Pure Chemical Industries, Ltd., model number: 169-07045), and mix for 3 minutes at an inclination angle of 30 ° and a rotation speed of 2 Or / m. Thus, a detergent composition containing a slipperiness improving agent for washing was obtained. Table 2 shows the slipperiness of the obtained detergent composition containing a slipperiness improver for washing. The washing water in which this was dissolved turned into a viscous solution, and was a detergent composition containing a slipperiness improver for washing with a very good skin feel after drying at a slipperiness rank: 5. The average value of the frayed threads of the five MA test cloths was 50.

(Example 9)

Water 370 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40 wt% No.2 silicate aqueous solution 50 kg, sodium carbonate 100 kg, sodium sulfate 147.5 kg, polyethylene glycol 5 kg, CBS dye 2. After mixing 5 kg, 25 kg zeolite and 100 kg sodium tripolyphosphate to prepare a homogeneous slurry, the slurry was spray-dried, and 4.0 kg of the resulting detergent composition was added to a concrete mixer (Koyo Machinery Industries, Ltd. Co., Ltd., capacity 40 L), then add 0.28 kg of potassium mesophosphate (Wako Pure Chemical Industries, Ltd., model number: 169-07045), tilt angle 30 °, rotation speed 20 The mixture was mixed at r / m for 3 minutes to obtain a detergent composition containing a slipperiness improving agent for washing. Table 2 shows the slipperiness of the obtained detergent composition containing a washability improver for washing. The washing water in which this was dissolved turned into a viscous solution, and was a slipperiness rank: 5, a detergent composition containing a slipperiness improver for washing, which had a very good skin feel after drying. The average value of the frayed threads of the five MA test cloths was 50.

(Example 10) 0.3 kg of potassium metaphosphate (Wako Pure Chemical Industries, Ltd., model number: 169-07045) and 0.3 kg of sodium sulfate are added to a high-speed mixer (manufactured by Mitsui Miike Co., Ltd., capacity 2 L, with jacket). kg, and the main shaft was stirred at 360 Or / m for 3 minutes, and then the mixture was extracted to obtain a laundry slipperiness improver mixture (potassium metaphosphate 50% by weight, sodium sulfate 50% by weight). Was.

Table 2 shows the slipperiness when the detergent compositions obtained in Comparative Examples 1 and 2 and the above-mentioned mixture for improving the slipperiness for washing were added at the ratio shown in Table 1 during hand washing. The washing liquid in which the detergent composition and the laundry slipperiness improver were dissolved was a viscous solution, was excellent in slipperiness, and had a very good skin feel after drying.

table 1

In the table, the molecular weight of polyethylene glycol is 13,000, the molecular weight of sodium polyacrylate is 10,000, and the molecular weight of acrylic acid-maleic acid copolymer (Na salt) is 70,000.

Table 2 Example Example mm m Male example

1 2 3 4 5 6 7 8 9 Sliding property 3 5 5 5 5 5 5 5 5 After 5-valent fiber ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Preparation of detergent composition

Water 370 kg, 50 wt% sodium dodecylbenzenesulfonate aqueous solution 200 kg, 40 wt% No. 2 silicate aqueous solution 50 kg, sodium carbonate 100 kg, sodium sulfate 147.5 kg, polyethylene glycol 5 kg, CBS type After mixing 2.5 kg of the fluorescent dye and 125 kg of zeolite to prepare a homogeneous slurry, the slurry was spray-dried to obtain a detergent composition.

(Example 11)

Potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045) was converted to a hammer rotation speed of 8500 r / m, using an atomizer (manufactured by Fuji Padal Co., Ltd., type A-7.5). Grinding was performed under the conditions of a raw material supply rate of 60 kg / hr and a screen diameter of 0.7 mm to obtain potassium metaphosphate having an average primary particle size of about 60 / m.

4.0 kg of the above detergent composition was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L). Then, 0.4 kg of the above ground potassium metaphosphate was added, and the tilt angle was 30 ° and the rotation was The mixture was mixed at several rZm for 3 minutes to obtain a detergent composition containing a slipperiness improving agent for washing. Table 3 shows the evaluation results of the obtained detergent composition containing the slipperiness improving agent for laundry. Immediately after dissolving this, the washing water becomes a viscous solution, slippery rank: 5, immersion response time 20 minutes (slippery rank after immersion: 4), residual adhesion to black cloth〇, after drying This was a detergent composition containing a slipperiness improving agent for washing, which had a very good skin feel.

(Example 12)

4.0 kg of the above detergent composition was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), followed by potassium metaphosphate (manufactured by Wako Pure Chemical Industries, Ltd., model number: 169-07045, average particle size) 0.4 kg in diameter, mixed at an inclination angle of 30 ° and a rotation speed of 20 rZm for 3 minutes to form a detergent composition containing a slipperiness improver for washing. I got something. Table 3 shows the evaluation results of the obtained detergent composition containing the slipperiness improving agent for laundry. Washing water immediately after dissolving this becomes a viscous solution, slipperiness rank: 5, immersion response time 120 minutes (slipperiness rank after immersion: 5), residual / adhesiveness to black cloth X, after drying This was a detergent composition containing a slipperiness improver for washing, which had a very good skin feel.

(Example 13)

Example 3 High-speed mixer (Mitsui Miike Co., Ltd., capacity 2 L, with jacket) 0.4 kg of ground potassium metaphosphate obtained by the same method as in Example 11 and sodium lauryl sulfate (Kao Co., Ltd.) , And Emar 10 powder) were poured into the jacket, and the jacket was agitated until the mixture temperature reached 70 at 3600 m while flowing warm water of 80 at 10 L / min through the jacket. Thereafter, 0.086 kg of polyethylene glycol (K-PEG6000, manufactured by Kao Corporation), which had been heated to 70 in advance, was added and stirring was continued for 3 minutes, after which the mixture was extracted. Next, the obtained mixture was extruded through a screen with a hole diameter of 0.5 mm using an extrusion granulator (Dalton Co., Ltd .: Dome Gran) to be consolidated. After the obtained extrudate is cooled, it is crushed by a sizing machine (Dalton Co., Ltd. power mill, screen diameter Φ 1. Omm), and adjusted to 700 m or less-355 / ^ m or more by classification. Then, a granular material for improving slipperiness for washing was obtained (70% by weight of potassium metaphosphate, 15% by weight of sodium lauryl sulfate, 15% by weight of polyethylene glycol).

Example 11 4.0 kg of the same detergent composition used in Example 1 was put into a concrete mixer (manufactured by Koyo Machinery Co., Ltd., capacity: 40 L). Was added thereto and mixed at an inclination angle of 30 ° and a rotation speed of 20 rZm for 3 minutes to obtain a detergent composition containing a granulating material for a laundry slipperiness improving agent. Table 3 shows the slipperiness of the obtained detergent composition containing the granulated material for washing. The wash water in which this was dissolved turned into a viscous solution, with a slipperiness rank of 5, and a soaking time of 60 minutes (after soaking) Slipperiness rank: 5) The detergent composition containing a granulation of a slipperiness improver for washing, which has very good residual / adhesiveness to black cloth and very good skin feel after drying.

(Example 14)

Example 3 High-speed mixer (Mitsui Miike Co., Ltd., capacity 2 L, with jacket) 0.4 kg of ground potassium metaphosphate obtained by the same method as in Example 11 and sodium lauryl sulfate (Kao Co., Ltd.) , And Emar 10 powder) were poured into the jacket, and the jacket was agitated at 3600 r / m until the mixture temperature reached 7 Ot: while flowing warm water at 80 at 10 LZ into the jacket. Thereafter, 0.086 kg of polyethylene glycol (K-PEG6000, manufactured by Kao Corporation) heated to 70 in advance was added and stirring was continued for 3 minutes, after which the mixture was extracted. Next, the resulting mixture is extruded into a granulator.

It was extruded through a screen with a hole diameter of 0.5 mm by a Dalton Co., Ltd. (Dome Gran) to consolidate. After cooling the obtained extrudate, it is pulverized with a sizing machine (Dalton Co., Ltd., power mill, screen diameter Φ1.5 mm), and adjusted to 1000 / m or less-355 / m or more by classification. Then, a granular material for improving slipperiness for washing (70% by weight of potassium metaphosphate, 15% by weight of sodium lauryl sulfate, 15% by weight of polyethylene glycol) was obtained.

Example 11 4.0 kg of the same detergent composition used in Example 1 was added to a concrete mixer.

(Manufactured by Koyo Machinery Co., Ltd., capacity: 40 L), followed by the addition of 0.57 kg of the above-mentioned granular material for improving smoothness for washing, at a tilt angle of 30 ° and a rotation speed of 20 rm for 3 minutes. The mixture was mixed to obtain a detergent composition containing a granulating material for a laundry slipperiness improving agent. Table 3 shows the slipperiness of the obtained detergent composition containing the granulated material for washing. The washing water in which this was dissolved turned into a viscous solution, with a slipperiness rank of 5, a immersion response time of 150 minutes (slippery rank after immersion: 5), residual adhesion to black cloth, and a dry skin feel. Was very good, and the detergent composition contained a granular material for improving smoothness for washing. (Example 15)

Implemented in a high-speed mixer (manufactured by Mitsui Miike Co., Ltd., capacity 2 L, with jacket) 11 0.4 kg of ground potassium mesophosphate obtained by the same method as in 11 and sodium lauryl sulfate (Kao Corporation ), 0.086 kg of Emar 10 powder) was added thereto, and the jacket was stirred at 3600 r / m until the mixture temperature reached 70 while flowing hot water at 80 at 10 L / min into the jacket. Thereafter, 0.086 kg of polyethylene glycol (K-PEG6000, manufactured by Kao Corporation) heated to 7 Ot: in advance was added, and the mixture was stirred for 3 minutes, and then the mixture was extracted. Next, the resulting mixture is extruded into a granulator.

The product was extruded through a screen with a hole diameter of 0.7 mm (Dalton Co., Ltd .: Dome Gran) and compacted. After cooling the obtained extrudate, it is pulverized with a sizing machine (Dalton Co., Ltd. power mill, screen diameter φ2.0 mm), and adjusted to 1410 zm or less-355 ^ m or more by classification. Then, a granulated laundry slipperiness improver (70% by weight of potassium metaphosphate, 15% by weight of sodium lauryl sulfate, and 15% by weight of polyethylene glycol) were obtained.

(Capacity: 40 L, manufactured by Koyo Machinery Co., Ltd.), followed by addition of 0.57 kg of the above-mentioned granulate for improving smoothness for washing, at an inclination angle of 30 ° and a rotation speed of 20 rZm for 3 minutes. The mixture was mixed to obtain a detergent composition containing a granulating material for a laundry slipperiness improving agent. Table 3 shows the slipperiness of the obtained detergent composition containing the granulated material for washing. The washing water in which this was dissolved turned into a viscous solution, with a slipperiness rank of 5, a soaking response time of 180 minutes (slippery rank after immersion: 5), residual adhesion to black cloth, and dry skin feel. This was a very good detergent composition containing a granular material for improving smoothness for washing.

Examples 16 to 26

Potassium metaphosphate was synthesized by the following method and evaluated for hand washing and washing.

KH ₂ P0 ₄ in (Sigma-Aldrich Japan KK, reagent special grade, L ot. A8347, KZP molar ratio = 1. 00), Κ / Ρ molar ratio of potassium metaphosphate after firing becomes a value shown in Table 4 as, H ₃ P0 ₄ (manufactured by Wako pure Chemical Industries, Ltd., special grade reagent, purity 85%, Lo t. CKL 22 18) was added, was calcined for 3 hours at a temperature shown in Table 4. The obtained calcined product was pulverized in a mortar to obtain potassium metaphosphate. 4.0 kg of the detergent composition obtained in Comparative Example 1 was put into a concrete mixer (manufactured by Koyo Kikai Sangyo Co., Ltd., capacity: 40 L). Subsequently, each potassium metaphosphate synthesized under the conditions shown in Table 4 was used. The components were added at the ratios shown in Table 4 (outside ratio of the detergent composition), and mixed at an inclination angle of 30 ° and a rotation speed of 2 Or / m for 3 minutes to obtain a detergent composition containing a slipperiness improving agent for washing. Table 4 shows the slipperiness of the obtained laundry detergent-containing detergent composition.

From the results in Table 4, when the slipperiness was evaluated by hand-washing evaluation, the KZP molar ratio was less than 1, indicating a better slipperiness rank. The slipperiness rank also changed with the firing temperature, and good slipperiness was shown at 40 Ot: or more.

The KZP molar ratio was determined according to the following measurement method. Measuring method of KZP molar ratio>

Samples 0. lg taken platinum Rutsupo, further L i ₂ B ₄ 0 ₇ a 5 g and, L i ₂ C0 ₃ with a release agent (weight ratio: L i B r: L i N0 3 = 5: 1: 0.5 g of 1) was added and melted at 1230 with a bead sampler (NT-2100, manufactured by Tokyo Kagaku Co., Ltd.) to produce a glass bead.

K and P in the glass beads were measured under the following conditions using a fluorescent X-ray device (Z SX IO e, manufactured by Rigaku Corporation) (XRF intensity).

X-ray source: Rh tube Voltage and current: 50 KV 50 mA Spectral crystal detector Angle

K: Li FSC (scintillation counter) 136.68 deg P: GePC (proportional counter) 141.19 deg

KZP molar ratio is calculated, KH ₂ P0 ₄ (Sigma-Aldrich Japan KK, reagent special grade) was measured in the same manner as the sample, as the basis for ΚΖΡ molar ratio 1.00, below kappa / [rho molar ratio of sample It was calculated by calculation.

XRF intensity of サンプル (sample) X X XRF intensity of (reagent)

κζρ molar ratio =

XRF intensity of Ρ (sample) X 強度 XRF intensity of (reagent) Table 4

The slipperiness improving agent and the slipperiness improving agent granules of the present invention are used for hand washing and washing clothes and the like. Above all, it is also suitably used in hand-washing, which is immersed for a long time.

By using the slipperiness improver for washing of the present invention, the slipperiness between the objects to be washed can be improved at the time of hand washing, so that the laundry can be washed with a light force and the speed of rubbing the laundry (the number of times of rubbing per hour) increases. This has the effect of facilitating hand washing. Furthermore, the use of the laundry slipperiness improver granules of the present invention does not cause potassium metaphosphate to remain undissolved or adhere to clothing. Similar effects are achieved. In addition, hand care by enhancing the feel of hand washing, and in washing machine washing, against damage to fibers caused by mechanical forces such as agitation, etc. This can provide an effect that clothing care can be provided when it can be avoided.

Claims

The scope of the claims

1. A slipperiness improver for laundry containing potassium phosphate.

2. The laundry slipperiness improver according to claim 1, wherein the KZP molar ratio of potassium metaphosphate is less than 1.

3. The slipperiness improver for washing according to claim 1 or 2, which is used for hand washing.

4. A detergent composition comprising the laundry slipperiness improver according to claim 1 and a solubilizer.

5. The detergent composition according to claim 4, wherein the amount of the solubilizing agent is at least 0.5 times equivalent to the amount of the replacement ion source in the potassium phosphate in the potassium phosphate.

6. The detergent composition according to claim 4, further comprising a surfactant and / or a builder.

7. The detergent composition according to claim 6, which contains, as a builder, a sequestering agent having a calcium ion trapping ability of 100 mg CaCO ₃ or more by 5% by weight or more.

8. The detergent composition according to claim 7, wherein the sequestering agent is a water-soluble organic substance.

9. The detergent composition according to claim 4, further comprising a silicate.

10. The detergent composition according to claim 9, wherein the gaylate is sodium silicate.

11. The detergent composition according to claim 4, further comprising a phosphate.

12. The detergent composition according to claim 11, wherein the phosphate is sodium tripolyphosphate.

13. Wash by hand washing under the condition of potassium metaphosphate concentration in water of 3 OmgZL or more and bath ratio of 2 or more.

14. Granules for washing with a slipperiness improver containing potassium metaphosphate.

15. The granular material for improving slipperiness for washing according to claim 14, wherein the average particle size of the potassium metaphosphate is from 0.5 / m to 200 inclusive.

16. The granular material for improving slipperiness according to claim 14, which is used for hand washing.

17. The granulated material according to claim 14, further comprising a binder substance.

18. The granulated slipperiness improver for laundry according to claim 17, wherein the binder substance is polyethylene glycol.

19. The granulated product of claim 14, having an average particle size of 100 or more and less than 2000; m.

20. The granulate for improving slipperiness according to claim 14, further comprising a solubilizing agent.

21. A detergent composition comprising the granularity improving agent for laundry according to claim 14 and a solubilizing agent.

22. A detergent composition comprising the laundry slipperiness improver granule according to claim 20.

23. The detergent composition according to claim 21, wherein the amount of the solubilizing agent is at least 0.5 equivalents to potassium ions in the potassium metaphosphate.

24. The detergent composition according to claim 21, further comprising a surfactant and / or a builder.