JPH1095998A - Granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a granular detergent composition especially having cleaning power of multifunctional type irrespective of kinds of clothes to be washed and stains, excellent in storage stability, readily masking an unpleasant smell and improved in biodegradability. SOLUTION: This detergent composition comprises (a) 5-40wt.% of an α- sulfofatty acid lower alkyl ester salt, (b) 7-30wt.% of a nonionic surfactant, (c) 2-20wt.% of a fatty acid soap and (d) an oil absorbing carrier. The ratio of the component (a)/the component (b) is 0.2 to 3.5 and that of the component (a)/the component (c) is 1.0-4.0. The composition further contains clay minerals and/or a nonionic gel agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention particularly has a multifunctional detergency irrespective of the type of cloth to be washed and stains, has excellent storage stability, easily masks unpleasant odors, The present invention relates to a granular detergent composition having good degradability.

[0002]

2. Description of the Related Art As is conventionally known, lower alkyl ester salts of α-sulfofatty acids are excellent in hard water resistance, have a sufficient detergency as an active ingredient of a detergent for clothes, and have a coating property. It has the characteristic of finishing the wash cloth with a good texture, but is inferior in foaming power to general-purpose surfactants such as linear alkylbenzene sulfonate, α-olefin sulfonate, or fatty acid soap (however, When a drum type washing machine is used, there is an excessive foaming power), and further, the rinsing property is poor, and there is a disadvantage that a lot of foam remains when rinsing. JP-A-49-66708 discloses a defoaming detergent compatible with a drum-type washing machine, comprising a combination of a lower alkyl ester salt of α-sulfofatty acid, a nonionic surfactant, and a fatty acid soap. However, it was not sufficient in terms of suppressing seepage of the nonionic surfactant. In addition, α-sulfofatty acid lower alkyl ester salts have a problem that they are hydrolyzed with the passage of time to cut the ester bond, and are converted into fatty acid sulfonated di-salts. This disalt has a problem that the detergency is inferior to that of the lower alkyl ester salt of α-sulfofatty acid, and thus the initial or predetermined period of detergency cannot be obtained.

[0003] JP-A-63-254198 discloses α
A method for producing a granular detergent in which a sulfo fatty acid lower alkyl ester salt is spray-dried so as not to come in contact with an alkali substance as much as possible to suppress hydrolysis of the α-sulfo fatty acid lower alkyl ester salt is disclosed. However, in the final detergent product, the lower alkyl ester salt of α-sulfofatty acid and the alkaline substance are adjacent to each other, and it is avoided that the lower alkyl ester salt of α-sulfofatty acid gradually hydrolyzes during the storage period. Absent. Also, Japanese Patent Application Laid-Open
No. 38708 discloses a phosphorus-free detergent excellent in detergency, which comprises a combination of an α-sulfo fatty acid lower alkyl ester salt, a nonionic surfactant and a fatty acid soap. However, even in this technique, there are problems in terms of suppression of hydrolysis and caking of the lower alkyl ester salt of α-sulfofatty acid during the storage period, suppression of exudation of the nonionic surfactant, further low-temperature solubility, and ease of masking. is there.

Japanese Patent Application Laid-Open No. 4-345700 discloses a mixture of particles containing a lower alkyl ester salt of α-sulfofatty acid and not containing an alkaline substance and particles containing an alkaline substance. Also, in the final detergent product, the lower alkyl ester salt of α-sulfofatty acid and the alkaline substance are adjacent to each other, and it is unavoidable that they gradually hydrolyze during the storage period. In addition, the detergent containing the α-sulfofatty acid lower alkyl ester salt is difficult to stabilize the crystal structure of the α-sulfofatty acid lower alkyl ester salt due to external factors such as moisture and temperature. Has also become a problem. Further, the lower alkyl ester salt of α-sulfofatty acid is hardly soluble in cold water of 10 ° C. or lower, and there is also a problem that a residue of the dissolution adheres to an object to be washed during washing in winter.

[0005] In addition, a detergent containing a lower alkyl ester salt of α-sulfofatty acid is decomposed with time and emits an unpleasant odor, thereby significantly reducing the commercial value. ing. In order to prevent this unpleasant odor, JP-A-50-151905 discloses that
Detergent compositions containing a hindered phenolic compound, borax, and sodium citrate have been proposed, but also cannot completely prevent the decomposition of the α-sulfo fatty acid lower alkyl ester salt. On the other hand, as a method of suppressing the odor, there is a method of masking by adding a fragrance. However, in the fragrance usually used for masking, an unpleasant odor caused by the decomposition of the α-sulfo fatty acid lower alkyl ester salt is masked. Is not enough.

[0006] Thus, α- has excellent surface activity.
In order to obtain a good-quality detergent composition containing a sulfo fatty acid lower alkyl ester salt, it is necessary to improve foam suppression, rinsing, hydrolysis inhibition, caking resistance, low-temperature solubility and odor prevention. On the other hand, nonionic surfactants generally have a low foaming property, the detergency is hardly affected by the hardness of water, and the nonionic surfactants are particularly excellent in mud dirt and dirt dispersibility at low temperatures.
Further, it is an excellent surfactant having good biodegradability, low environmental load, low toxicity, and no problem in safety. However, since nonionic surfactants are generally liquid at room temperature, there has conventionally been a problem of exuding nonionic surfactants from nonionic granular detergent products into detergent containers. When the nonionic surfactant seeps into the detergent container,
Not only does the appearance of the product deteriorate, but also the detergency decreases due to the decrease in nonionic surfactant at the container contact area, and the fluidity and caking resistance of the detergent particles are adversely affected. In addition, since the nonionic surfactant is weak to heat, the conventionally used method of spray-drying and manufacturing a mixed slurry of the surfactant and the cleaning builder causes the nonionic surfactant to thermally decompose as exhaust gas. Since it is released into the atmosphere, it may cause environmental destruction such as air pollution, which is not preferable.

In Japanese Patent Application Laid-Open No. 4-339898, an attempt is made to improve the prevention of exudation of a nonionic surfactant by incorporating 5 to 20% of an amorphous oil-absorbing carrier.
Since the nonionic surfactant itself is still liquid at room temperature, the nonionic surfactant exudes particularly in summertime exceeding 30 ° C., which causes a problem that the fluidity of the detergent particles is deteriorated. In Japanese Patent Application Laid-Open No. 5-125400, a nonionic surfactant is charged into a dry granulation device together with an oil-absorbing carrier without spray drying, and granulation is performed without giving excessive heat. A method is disclosed in which the surface of detergent particles is coated with silica to suppress deterioration in fluidity due to moisture absorption. However, even if the surface of the detergent particles is protected with amorphous silica, if the detergent particles are placed in a high-humidity environment for a long time, the detergent particles will gradually absorb moisture, and the problem that the fluidity and the anti-caking property deteriorates. Still remains.

In Japanese Patent Application Laid-Open No. Sho 62-54799, the surface of granular nonionic detergent particles is coated with PEG to suppress the exudation of the nonionic surfactant, but PEG has an affinity for water. Therefore, when the detergent particles are placed in a high humidity environment, the surface of the detergent particles is in a melted state, and as a result, the fluidity of the detergent particles is deteriorated. On the other hand, fatty acid soaps, which are alkali metal salts of fatty acids, have been widely used as detergents for bathing, hand washing, and clothes washing since ancient times, because they have excellent detergency, rinsing properties, skin irritation and safety. It's being used. However, in the case of this fatty acid soap,
It itself has poor solubility in cold water, and furthermore has the disadvantage that it reacts with calcium, magnesium or iron ions, especially in hard water, to form a water-insoluble divalent metal soap, so-called scum, causing various harmful effects.

Japanese Patent Application Laid-Open No. 54-15911 discloses a method of improving dispersibility, detergency and foaming power by adding a nonionic surfactant and a lower alkyl ester salt of α-sulfofatty acid to a fatty acid soap. However, they were insufficient in terms of mud stain cleaning power, oil stain cleaning power, low-temperature solubility, anti-caking properties, and suppression of hydrolysis of α-sulfo fatty acid lower alkyl ester salts. Also, Japanese Patent Application Laid-Open No. 5-2953
No. 99 discloses that by adding a nonionic surfactant and an alkyl sulfate salt to a fatty acid soap, low-temperature solubility, detergency in hard water, and biodegradability are improved. , Mud dirt cleaning power, oil dirt cleaning power,
And low-temperature solubility. In addition, Japanese Unexamined Patent Application Publication No.
JP-A-227700 discloses that an anionic surfactant represented by sodium alkylbenzenesulfonate and sodium alkylsulfate, a nonionic surfactant, and a fatty acid soap were blended in a specific amount and in a specific ratio.
High bulk density detergent compositions with improved distribution characteristics (solubility in water at 10-20 ° C) and solidification are disclosed.
However, when the lower alkyl ester salt of α-sulfofatty acid is used as the anionic surfactant, the suppression of hydrolysis of the lower alkyl ester salt of α-sulfofatty acid, the masking property of unpleasant odor, and the solubility at a low temperature of 10 ° C. or lower Further, it did not occur with detergents containing α-sulfo fatty acid lower alkyl ester salts, nonionic surfactants, and fatty acid soaps alone. Due to stickiness of intermediate products or final products during production, adhesion to production equipment, etc. There was a problem in the point.

Further, Japanese Patent Application Laid-Open No. 3-265699, 4-1
Nos. 1699 and 6-192,976 disclose a granular detergent composition containing a small amount of a lower alkyl ester salt of α-sulfofatty acid, a nonionic surfactant, a fatty acid soap and amorphous silica. The tackiness that occurs when a large amount of surfactants are used in combination has not been eliminated. As described above, the α-sulfo fatty acid lower alkyl ester salt, the nonionic surfactant, and the fatty acid soap have characteristic washing performance, but have many drawbacks in use. By the way, in the latter half of the 1980's, high bulk density type granular detergents, so-called ultra-compact detergents, appeared in Japan, and have been accepted by consumers up to the present, and there is a growing demand for more compact detergents in the future.

In recent years, with the spread of large-scale fully automatic washing machines (including water-saving types) and the emergence of drum-type washing machines (also called front-loading types), more multifunctional washing machines have been developed.
For example, a detergent having a good rinsing property corresponding to a water-saving type fully automatic washing machine is desired, and a detergent having a low foaming property corresponding to a drum type washing machine is desired. In recent years, abnormal weather, including global warming, has become an important issue.However, in the field of detergents, even if the weather is left for a long period of time under dramatic changes in weather conditions such as temperature and humidity, the quality of More and more people have heard of a desire for a detergent that does not suffer from deterioration (e.g., caking, seepage, deterioration of cleaning components, etc.). Further, as environmental problems are being called out, there is an increasing demand for detergents having a low environmental load, that is, having good biodegradability.

[0012]

Accordingly, the present invention has a multifunctional detergency irrespective of the type of cloth to be washed and stains, has good rinsing properties, has excellent storage stability, and is unpleasant. An object of the present invention is to provide a granular detergent composition which has a low odor, is easy to mask, has good biodegradability, and can be produced stably.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, among the anionic surfactants which are generally said to have excellent detergency against cotton cloth and oil stains, Α-Sulfo fatty acid lower alkyl ester salt with low critical micelle concentration (cmc) and good biodegradability, and nonionic surface activity with good biodegradability and excellent detergency against chemical fibers, mud stains and oil stains If the agent and fatty acid soap excellent in rinsing and biodegradability are blended in a specific amount, α-sulfo fatty acid lower alkyl ester salt, nonionic surfactant, without impairing the respective cleaning properties of the fatty acid soap, It has been found that it is possible to obtain a detergent having a multifunctional detergency irrespective of the type of cloth to be washed and stains, and having good rinsing properties. Furthermore, surprisingly,
Less unpleasant odor and easy masking by combining α-sulfo fatty acid lower alkyl ester salt with strong ester odor, nonionic surfactant with strong alcohol odor, and fatty acid soap with strong soap odor in a specific ratio And furthermore, the improvement of the caking resistance during the storage period,
It has been found that it is possible to suppress the exudation of the nonionic surfactant and to suppress the deterioration of the lower alkyl ester salt of α-sulfofatty acid, and to stabilize the detergency over time. Where α
-Sulfo fatty acid lower alkyl ester salt, nonionic surfactant, and detergents containing fatty acid soaps alone, which did not occur, the stickiness of intermediate products or final products in the course of production was reduced by α-sulfo fatty acid lower alkyl ester salt. When a nonionic surfactant and a fatty acid soap are used in combination, the intermediate product or the final product in the course of production becomes sticky, so that it easily adheres to the production equipment, and there is a problem in maintaining stable production. If a certain type of oil-absorbing carrier is added to the mixture, such stickiness can be suppressed, and stable production can be continued regardless of a specific production method. The present invention has been made based on the above-described new findings.

That is, a straight-chain alkylbenzene sulfonate (commonly called LAS) or α-olefin sulfonate (commonly called AOS), which is relatively inferior in biodegradability, is used as a main surface active ingredient, and α-sulfo fatty acid lower alkyl ester salt ,
Nonionic surfactants and fatty acid soaps can be used only as mere additives, whereas the present invention has excellent washing performance, but it is difficult to handle α-sulfo fatty acid lower alkyl ester salt and nonionic surfactant. Having a surfactant and a fatty acid soap as main surfactants, and compounding it in a specific amount and ratio, it has a multifunctional detergency regardless of the type of cloth to be washed and stains, and has good rinsing properties. In addition, it was found that the biodegradability was good, and in addition, the storage stability was improved, the unpleasant odor was reduced, and the masking was facilitated. In addition, the stickiness produced when the above three surfactants were used in combination In that it provides a composition that is easy to produce.

That is, the present invention comprises the following components: (a) α-sulfofatty acid lower alkyl ester salt:
A particulate detergent composition comprising: 40% by weight; (b) a nonionic surfactant: 7 to 30% by weight; (c) a fatty acid soap: 2 to 20% by weight; and (d) an oil-absorbing carrier. a) / (b) (weight ratio) = 0.2-3.5, and (a) / (c) (weight ratio) = 1.0-4.0 The present invention relates to a detergent composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The α-sulfofatty acid lower alkyl ester salt, which is the component (a) of the present invention, is also called a sulfonate of a fatty acid lower alkyl ester and is generally represented by the following formula.

[0017]

Embedded image Here, R ₁ has 8 to 22 carbon atoms, preferably 10 carbon atoms.
20, particularly preferably a straight-chain or branched alkyl or alkenyl group of 12 to 18, R ₂ is 1 to 6 carbon atoms, preferably 1 to 3, especially straight-chain, preferably 1 to 2 Or a branched lower alkyl group, and M is an alkali metal or ammonium. Specific examples of the alkyl group as R ₁ include, for example, an octyl group, a decyl group,
And alkyl groups such as dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and docosyl group. On the other hand, specific examples of the alkenyl group as R ₁ include, for example, a dodecynyl group, a tetradecynyl group,
Alkenyl groups such as a hexadecynyl group, an octadecynyl group, an eicosinyl group and the like can be mentioned. Preferred alkyl groups are, for example, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and preferred alkenyl groups include, for example, tetradecynyl group, hexadecynyl group, octadecynyl group and the like.

Specific examples of the alkyl group as R ₂ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group and a t-butyl group.
Examples thereof include a butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and an isohexyl group. Specific examples of the alkali metal as M include, for example, lithium, sodium, and potassium. Preferably, M is sodium, potassium, or the like. The α-sulfo fatty acid lower alkyl ester salt is usually obtained by a known production method. For example, a lower alkyl ester of a fatty acid is sulfonated with sulfuric anhydride using a conventional continuous thin film type sulfonation apparatus or tank type sulfonation apparatus, and then ripened and bleached as necessary, and then neutralized. Alternatively, there may be mentioned a method in which a fatty acid is sulfonated by any of the above-mentioned devices, esterified with a lower alcohol, and then neutralized.

As the fatty acid or fatty acid ester used as a raw material, a fatty acid or ester thereof derived from natural fats and oils (for example, beef tallow, coconut oil, palm oil, palm kernel oil, etc.) can be used, and alcohol or olefin can be used. Synthetic esters or esters thereof can be used. In the present invention, the α-sulfofatty acid lower alkyl ester salt is contained in an amount of 5 to 40% by weight, preferably 7 to 35% by weight, more preferably 9 to 30% by weight, based on the weight of the granular detergent composition. You. This amount is 5
When the amount is less than the weight%, the cleaning power for the cotton cloth is undesirably reduced. On the other hand, if it exceeds 40% by weight, the obtained detergent particles are liable to cause caking during the storage period, which is not preferable. As the nonionic surfactant which is the component (b) of the present invention, various nonionic surfactants can be used. Preferred nonionic surfactants include, for example, the following. (1) An aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms and an alkylene oxide having 2 to 4 carbon atoms on average 3
Polyoxyalkylene alkyl (or alkenyl) ether added to ３０30 mol, preferably 7-20 mol. Among them, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
Here, the aliphatic alcohol may be a primary alcohol or a secondary alcohol, and the alkyl group may have a branched chain, but a primary alcohol can be preferably used. (2) polyoxyethylene alkyl (or alkenyl)
Phenyl ether. (3) A fatty acid alkyl ester alkoxylate represented by the following formula in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.

R ₁ CO (OA) n OR ₂ (R ₁ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents a fatty acid residue having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide; It preferably represents an addition unit of alkylene oxide of 2 to 3. n represents an average number of added moles of alkylene oxide, and generally represents 3 to 3
0, preferably a number from 7 to 20. R ₂ has 1 carbon atom
Represents a lower alkyl group which may have a substituent. (4) Polyoxyethylene sorbitan fatty acid esters. (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid esters. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester. (9) fatty acid alkanolamides.

Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and an HLB of 9 to 16; Fatty acid methyl ester ethoxylate in which ethylene oxide is added to an ester is particularly preferably used. Further, these nonionic surfactants may be used as a mixture. In the present invention,
The nonionic surfactant is contained in an amount of 7 to 30% by weight, preferably 10 to 27% by weight, more preferably 15 to 25% by weight, based on the weight of the granular detergent composition. This amount is 7
If the amount is less than% by weight, the detergency of mud stains, oil stains, and chemical fibers decreases, which is not preferable. On the other hand, if it exceeds 30% by weight, the nonionic surfactant tends to exude from the detergent particles obtained during the storage period, which is not preferable.

The fatty acid soap which is the component (c) of the present invention has an alkyl group or an alkenyl group having 7 to 2 carbon atoms.
1, preferably 9 to 19, more preferably 11 to 17 alkali metal salts of fatty acids, particularly preferably sodium salts and potassium salts are used. Examples of the fatty acids include, for example, synthetic fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, caproleic acid, laurolic acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid. Fatty acids of animal and vegetable oils such as coconut oil, palm kernel oil, palm oil, soybean oil, rice bran oil, rapeseed oil, coconut oil, pork oil, tallow, etc., or hardened oils of these animal and vegetable oils, hardened oils such as fish oil Further, natural fatty acids such as the above-mentioned transesterified oils of animal and vegetable oils and fats and the fatty acids of fractionated oils may be mentioned, and these are produced by directly saponifying them or neutralizing fatty acids or synthetic fatty acids derived therefrom.

In the present invention, the fatty acid soap is contained in an amount of 2 to 20% by weight, preferably 3 to 18% by weight, more preferably 4 to 13% by weight based on the weight of the granular detergent composition. If the amount is less than 2% by weight, it is not preferable because foaming during rinsing deteriorates. On the other hand, when the content exceeds 20% by weight, the solubility of the obtained detergent particles at low temperatures is undesirably deteriorated. In the present invention, the weight ratio of the components (a), (b) and (c) is important. In particular,
The weight ratio of the components (a) and (b) is (a) / (b)
= 0.2-3.5, preferably 0.3-3.0, more preferably
Must be between 0.4 and 2.5. (A) / (b) is 0.2
If it is less than 10%, masking of the odor generated from the obtained detergent becomes difficult, which is not preferable. On the other hand, (a) / (b)
Is more than 3.5, it is difficult to suppress the hydrolysis of the lower alkyl ester salt of α-sulfofatty acid during the storage period, and it is not preferable because caking tends to occur during the storage period.

The weight ratio of component (a) to component (c) is (a) / (c) = 1.0-4.0, preferably 1.2-3.0.
8, more preferably from 1.5 to 3.3.
When the ratio (a) / (c) is less than 1.0, the solubility of the obtained detergent particles at low temperature is unfavorably deteriorated. On the other hand, (a) /
When (c) is more than 4.0, the solubility of the obtained detergent particles at low temperature is deteriorated, and it is difficult to mask the odor generated from the obtained detergent. By the way, α-sulfofatty acid lower alkyl ester salt, nonionic surfactant, non-detergent containing fatty acid soap did not occur. When a salt, a nonionic surfactant, and a fatty acid soap are used in combination, a noticeable tackiness is likely to occur in an intermediate product or a final product in the course of production, so that the granular detergent composition easily adheres to a production apparatus, As a result, it tends to be a problem in maintaining stable production. However, such a problem can be solved by adding a certain oil-absorbing carrier to these components. Therefore, stable production can be continued without choosing a specific manufacturing method. Further, when an oil-absorbing carrier is blended, deterioration of the masking property during the storage period of the detergent can be reduced.

The oil-absorbing carrier used in the present invention is added in order to improve the stickiness of the intermediate product or the final product and the deterioration with time of the masking property as described above. As such an oil-absorbing carrier, JIS-K51
Oil absorption amount expressed by 01 test method is 100ml / 100g
As described above, a substance having a content of preferably 150 ml / 100 g or more, more preferably 200 ml / 100 g or more, is suitably used. As such an oil-absorbing carrier, for example, as a silicate compound, Tokusil N (manufactured by Tokuyama Corporation)
Oil absorption amount 280ml / 100g), Nip seal NS-K
(Nippon Silica Co., Ltd., oil absorption 320ml / 100
g), Sylysia # 310 (Fuji Silysia Chemical Ltd.)
Aerosil # 300, such as amorphous hydrous amorphous silicic acid such as Sildex H-52 (manufactured by Asahi Glass Co., Ltd., oil absorption 260 ml / 100 g). (Nippon Aerosil Co., Ltd.
Amorphous anhydrous silicic acid such as oil-absorbing amount 350 ml / 100 g), petal-like hydrous amorphous calcium silicate such as Florite R (manufactured by Tokuyama Corporation, oil-absorbing amount 600 ml / 100 g), zonotlite (Ube Chemical ( Co., Ltd., oil absorption 2
Needle-like hydrated crystalline calcium silicate, such as 20 ml / 100 g), amorphous aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., oil absorption 170 ml / 100 g), and magnesium silicate (oil absorption 180 ml / 100 g). As carbonate compounds, magnesium carbonate (manufactured by Tokuyama Corporation, oil absorption 150 ml / 100 g), calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., oil absorption 110 ml / 100 g), and as other compounds, ultrafine spinel (Sumitomo Cement) (stock)
, Oil absorption 600ml / 100g), ultrafine cordierite (Sumitomo Cement Co., Ltd., oil absorption 600ml /
100g), ultrafine mullite (Sumitomo Cement Co., Ltd.)
Oil absorption 560 ml / 100 g), modified starch pine flow S (Matsuya Chemical Co., Ltd., oil absorption 130 ml / 100)
g) and the like. These oil-absorbing carriers may be used as a mixture.

The oil-absorbing carrier is preferably 2 to 20% by weight, particularly preferably 5 to 20% by weight, based on the weight of the granular detergent composition.
-15% by weight. If this amount is less than 2% by weight, the effect of improving the tackiness and masking properties is poor.
When the oil-absorbing carrier is used in an amount of 20% by weight, it is sufficient to improve the tackiness and masking properties. A compounding amount of more than 20% by weight is not required, and it is preferable to add another detergent component. Further, in the granular detergent composition of the present invention, if necessary, a component for immobilizing a nonionic surfactant such as a clay mineral or a nonionic gelling agent may be blended.
The addition of these components is effective in ensuring good flowability of the detergent particles at high temperatures and caking resistance, and this effect is due to the content of the nonionic surfactant in the granular detergent composition. When the content exceeds 15% by weight, it appears remarkably.

As the clay mineral used in the preferred embodiment of the present invention, a clay mineral belonging to the smectite group and having a three-layered dioctahedral or trioctahedral crystal structure is preferably used. Can be. Such a clay mineral has a cleavage property and has a layered structure. This clay mineral has a smaller oil absorption amount than the above oil absorbing carrier. In addition, the clay mineral has a property that nonionic surfactant forms chemical adsorption by hydrogen bonding between crystal layers and is fixed inside the clay mineral. By using this clay mineral, especially when the nonionic surfactant is contained in an amount of 15% by weight or more, the flowability and the caking resistance of the detergent particles at high temperatures are greatly improved. The clay mineral has a property of swelling as the nonionic surfactant is retained inside. The clay mineral that can be preferably used in the present invention preferably has an oil absorption of 80 ml /
Less than 100 g, more preferably 30 to 70 ml / 100
g.

Specific examples of such clay minerals include, for example, montmorillonite (oil absorption: 50 ml / 100) as a clay mineral having a dioctahedral type three-layer structure.
g), nontronite (oil absorption: 40 ml / 100
g), beidellite (oil absorption: 62 ml / 100 g),
Pyrophyllite (oil absorption: 70 ml / 100 g) and the like. On the other hand, as a clay mineral having a trioctahedral type three-layer structure, saponite (oil absorption: 73 ml / 1
00g), hectorite (oil absorption: 72 ml / 100)
g), Stephen site (oil absorption: 30 ml / 100
g), talc (oil absorption: 70 ml / 100 g) and the like. These clay minerals generally include those naturally produced and those artificially hydrothermally synthesized, but are not particularly limited. In such a clay mineral, a peak derived from the spread of the clay layer detected at 10 to 20 angstroms in X-ray diffraction analysis and a peak derived from the three-layer structure of the clay detected at 4 to 5 angstroms developed. Anything can be used without particular limitation. On the other hand, clay minerals, especially in the case of natural products, may contain many impurities such as quartz, cristobalite, calcite, opal and feldspar, and those having many impurities are not suitable for the present invention and have a purity of at least 60. %, More preferably 70% or more, and most preferably 100%. Particularly preferably used clay minerals include Na-type montmorillonite, Ca-type montmorillonite, activated bentonite (Na / Ca-type montmorillonite), Na-type hectorite, and Ca-type hectorite.

The nonionic gelling agent used in the present invention comprises:
It has the property of gelling a nonionic surfactant and fixing and retaining the nonionic surfactant in a granular detergent. The use of this nonionic gelling agent greatly improves the flowability and caking resistance of detergent particles at high temperatures, especially when the nonionic surfactant is contained in an amount of 15% by weight or more. Therefore, various nonionic gelling agents can be used as long as the nonionic gelling agent has such a function. As the nonionic gelling agent used in the present invention, those similar to those conventionally used as oil gelling agents can be used. Among such nonionic gelling agents, those having a maximum compressive stress of 30 g / cm ² or more at 40 ° C. when a specific nonionic surfactant is gelled by the nonionic gelling agent are preferably used. This maximum compressive stress is caused by alcohol ethoxylate type nonionic surfactant (carbon chain length 1) which is a general detergent.
2, average number of moles of ethylene oxide added 9, melting point 20
) Is mixed with the nonionic gelling agent to be measured at 70 ° C in a 5/1 weight ratio, cooled to 20 ° C, and then
After leaving at 3 ° C. for 3 hours, a rectangular parallelepiped test piece having a length of 5 cm × width 5 cm × height 1 cm was prepared.
5cm cylindrical jig at 40 ° C and compression speed 20mm
The maximum compressive stress when pressed under the condition of / min is measured.

In the present invention, the nonionic gelling agent
The maximum compressive stress under the above conditions is 30 g / cm^Two Less than
Tendency of the detergent particles to be insufficiently fluid at high temperatures
There is. Further preferred maximum compressive stress is 50 to 2000
g / cm^Two The particularly preferred maximum compressive stress is 100 to 150.
0g / cm^Two It is. Preferred nonions that can be used in the present invention
Examples of the gelling agent include 12-hydroxystearyl
Acid (Maximum compressive stress 520g / cm^Two ) (KF Trading
Hydroxystearin (trade name), dibenzylide
Sorbitol (maximum compressive stress 30g / cm^Two ) (New Japan Science
Gel All D (trade name)), lithium stearate
(Maximum compressive stress 50g / cm^Two ) (L made by KF Trading
i-ST (trade name)), aluminum palmitate (most
Large compressive stress 50g / cm^Two ) (AL- made by KF Trading)
PL (trade name)), lithium 2-ethylhexanoate (most
Large compressive stress 66g / cm ^Two ) (KF Trading Li-
2EH (trade name)), 12-hydroxystearic acid
Luminium (Maximum compressive stress 126g / cm^Two ) (KF tray
Al-OHST (trade name), Lauroyl
Glutamic acid dibutylamide (Maximum compressive stress 200g / cm
^Two ) (Ajinomoto Coagulant GP-1 (trade name))
Uroylglutamic acid stearylamide (maximum compressive stress
53g / cm^Two ) (Made by Ajinomoto), dicaproyl lysine lauri
Luamide (maximum compressive stress 183g / cm^Two ) (Made by Ajinomoto),
Dicaproyl lysine lauryl ester (maximum compressive stress 4
5g / cm^Two ) (Made by Ajinomoto), lauroylphenylalanine
Laurylamide (maximum compressive stress 37g / cm^Two ) (Ajinomoto
Manufactured), polystyrene polybutadiene block copolymer
(Molecular weight: 200,000, composition: styrene / butadiene = 40
/ 60) (maximum compressive stress 60g / cm^Two ) (KF Trading
KF21 (trade name), polyacrylamide
(Molecular weight: 100,000)-Isoparaffin mixture (maximum compression
83g / cm stress^Two ) (Soragam S manufactured by Fuso Corporation)
D401 (trade name)), polystyrene block and polyb
Block copolymer of tadiene block (molecular weight: 10
10,000, composition: styrene / butadiene = 30/70) (maximum)
Compressive stress 48g / cm^Two ) (Made by KF Trading), Deki
Strin palmitic acid ester (Maximum compressive stress 80g / cm
^Two ) (Chiba Flour Leopard KL (trade name)), etc., or
These mixtures can be mentioned. These nonio
The desired maximum compressive stress can be obtained by mixing the gelling agent.
Can be provided.

In the granular detergent composition of the present invention, various components can be used without any particular limitation as long as they are optional components usually blended in detergent raw materials. For example, the following components can be blended as such components. (1) As an alkali washing builder, sodium carbonate,
Sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium potassium carbonate, sodium silicate, potassium silicate, layered sodium silicate and the like. (2) As chelate builders, sodium aluminosilicate, potassium aluminosilicate, sodium tripolyphosphate, sodium pyrophosphate, sodium polyacrylate, maleic acid-acrylic acid copolymer, NTA, ED
TA etc. (3) As anionic surfactants, linear alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfates, alkyl ether sulfates and the like. (4) As a cationic surfactant, distearyl dimethyl ammonium chloride, dioleyl dimethyl ammonium chloride and the like. (5) As a fluorescent agent, bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X] and the like. (6) As enzymes, lipase, protease, cellulase, amylase and the like. (7) Bleaching agents such as percarbonates and perborates. (8) As a bleach activator, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzenecarboxylic acid and the like. (9) As surface modifiers, finely divided calcium carbonate, finely divided zeolite, finely divided silica, finely divided alumina, finely divided starch,
Bentonite, polyethylene glycol, etc. (10) Polyethylene glycol, sodium carboxymethylcellulose, polyvinyl alcohol and the like as a re-contamination inhibitor. (11) As extenders, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like. (12) As a reducing agent, sodium sulfite, potassium sulfite and the like. (13) Silicone oil, silicone compound, etc. as a foam inhibitor. (14) Fragrances (15) Pigments These optional components can be blended into the granular detergent composition of the present invention by various blending methods. For example, these components may be blended in the granulation step, or may be mixed with the detergent particles obtained by the granulation treatment.

Next, a method for producing the granular detergent composition of the present invention will be described below. However, the granular detergent composition of the present invention is not limited by the following production method. 1. Kneading and extrusion of α-sulfo fatty acid lower alkyl ester salt, fatty acid soap, nonionic surfactant, oil-absorbing carrier, and, if necessary, clay mineral, optional components such as washing builder, fluorescent agent, etc. by kneader, extruder, etc. After being introduced into a mill and mixing while applying a shearing force therein to form a granulated product (solid detergent), the solid detergent is mixed with a crushing granulator such as a cutter mill in the presence of a grinding aid. After crushed into a granular detergent having a target particle size, it is introduced into a tumbling drum and mixed with an optional component such as an enzyme or a fragrance to obtain a bulk density of 0.5.
A method for producing a detergent composition having a g / cm ³ or more, preferably 0.6 g / cm ³ or more. 2. Optional components such as α-sulfo fatty acid lower alkyl ester salt, fatty acid soap, nonionic surfactant, oil-absorbing carrier, and, if necessary, nonionic gelling agent, washing builder, fluorescent agent, etc. , A Reidige mixer, a Henschel mixer, etc., into an internal stirring type granulator, stirring and granulating to make a granular detergent of the target particle size, and then introducing it to a rolling drum, and optionally for enzymes, fragrances, etc. A method for producing a detergent composition having a bulk density of 0.5 g / cm ³ or more, preferably g / cm ³ or more, by mixing with a component. 3. Granulate surfactant particles containing an α-sulfo fatty acid lower alkyl ester salt and a fatty acid soap, while a nonionic surfactant, an oil-absorbing carrier, and, if necessary, a clay mineral or a nonionic gelling agent A method for producing a detergent composition by granulating a granular nonionic detergent composition containing the same, introducing the granulated nonionic detergent composition into a rolling drum, and mixing with an optional component such as an enzyme or a fragrance. 4. Granulate surfactant particles containing a lower alkyl ester salt of α-sulfofatty acid and a small amount of a nonionic surfactant, while dispersing a fatty acid soap, an oil-absorbing carrier and, if necessary, a clay mineral. Alternatively, a method of producing a detergent composition by granulating a granular nonionic detergent composition containing a nonionic gelling agent, introducing them into a tumbling drum, and mixing them with optional components such as enzymes and fragrances. 5. Granulate the surfactant particles containing the lower alkyl ester salt of α-sulfofatty acid and the oil-absorbing carrier, while using a nonionic surfactant, a fatty acid soap and, if necessary, a clay mineral or a nonionic gelling agent. A method for producing a detergent composition by granulating a granular nonionic detergent composition containing the same, introducing the granulated nonionic detergent composition into a rolling drum, and mixing with an optional component such as an enzyme or a fragrance. For the detergent particles thus produced, for example,
The coating treatment may be performed by adding a coating agent in a tumbling drum. Thereby, the flow characteristics can be further improved. As the coating agent, JIS200
Fine powder having a mesh sieve passing amount of 50% or more is suitable. For example, the material is a carbonate such as sodium carbonate, calcium carbonate, magnesium carbonate, or a silicate such as amorphous silica, calcium silicate, magnesium silicate, or the like. , Zeolite, silica-alumina, aluminosilicates such as mullite,
Clay minerals such as bentonite, talc and hectorite, pigments such as titanium oxide, mica, and boron nitride, processed starch, cellulose ether, and the like can be used. The coating agent is generally present in the granular detergent composition of the present invention.
It is used in an amount of 0.5 to 15% by weight, preferably 1 to 10% by weight.

Enzymes, fragrances and the like can be added later to the detergent particles thus produced. The obtained granular detergent composition of the present invention has an average particle diameter of 300 to 2000.
μm, preferably 350 to 1500 μm, particularly preferably 400 to 1000 μm, and a bulk density of 0.5 to 1.2 g /
cm ³ , preferably 0.6 to 1.1 g / cm ³ , particularly preferably 0.6 g / cm ³ .
It is 65-1.0 g / cm ³ .

[0034]

The present invention will be described below in more detail with reference to examples and comparative examples. However, in the examples and comparative examples, each sample was evaluated by the following test methods. In addition,
The storage conditions of the detergent performed prior to the following tests are as follows. [Preservation test of detergent] Coated cardboard (basis weight: 3)
50 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ). × 1.2 kg of detergent was put in a box having a height of 18.5 cm and stored in a thermo-hygrostat at 35 ° C. and 85% RH for 4 weeks.

[Detergency test] A clean cotton cloth (Cotton No. 60 designated by the Japan Oil Chemistry Association,
5 × 5 cm), a white acrylic cloth (5 × 5 cm), and a white nylon cloth (5 × 5 cm) were immersed, and water was squeezed with two rubber rolls to even out the amount of stain. 10 pieces of this dirty cloth
After drying at 5 ° C. for 30 minutes, the surface of the cloth was rubbed left and right 25 times. Among them, those having a reflectance of 42 ± 2% were used as dirty cloths. 60 pieces of this dirty cloth (20 pieces of cotton cloth, 20 pieces of acrylic cloth)
Sheets, 20 pieces of nylon cloth) and 15 g of a sample detergent (detergent particles immediately after production and detergent particles after storage) were put into a two-tub washing machine (CW-225 type, manufactured by Mitsubishi Electric Corp.), and the mixture was heated at 15 ° C. 30
After washing with 10 liters of water (3 ° DH) for 10 minutes,
Dehydrated for 1 minute. Then, rinsing with 30 liters of water at 15 ° C. for 3 minutes and dehydration for 1 minute were repeated twice. Then, after the cloth to be washed was air-dried indoors for 48 hours, the reflectance of this cloth to be washed was measured, and the cleaning rate was calculated by the following equation. Cleaning rate (%) = ｛(K / S of dirty cloth−K / S of cleaning cloth)
/ (K / S of soiled cloth-K / S of unsoiled cloth)｝ × 100 Here, K / S is represented by the following equation. K / S = (1-R / 100) ² / 2R / 100 (Kuberka-Munk formula) Soil component % oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2. 5 Cholesterol 2.5 Gelatin 7.0 Inorganic dirt 29.85 Carbon black (designated by Japan Oil Chemicals Association) 0.5 [Measurement of rate of increase in hydrolysis of lower alkyl ester salt of α-sulfofatty acid] Measure the amount of anionic surfactant The total amount M of the α-sulfofatty acid lower alkyl ester disalt and the anionic surfactant is determined from a predetermined blending ratio of the anionic surfactant. Next, the detergent composition was adjusted to pH 1
1. Treatment with a 90% ethanol solution at 50 ° C. to separate the α-sulfofatty acid lower alkyl ester disalt as an insoluble matter, determine the amount S of the disalt by the methylene blue backdrop method, and determine the hydrolysis rate D according to the following equation. Ask. D (%) = (S / M) × 100 By the above operation, the hydrolysis rate was determined for the detergent particles immediately after production and for the detergent particles after storage, and the hydrolysis increase rate was calculated by the following equation. Hydrolysis increase rate (%) = hydrolysis rate after storage-hydrolysis rate immediately after production

[Rinseability test] In a two-tub washing machine (CW-225 type, manufactured by Mitsubishi Electric Corp.), 30 liters of water (3 ° DH) at 15 ° C., 15 g of a sample, and 12 cotton towels , And washed for 10 minutes, and then dehydrated for 1 minute. Then, the sample was rinsed with 30 liters of water at 15 ° C. for 3 minutes and dehydrated for 1 minute, and further rinsed with 30 liters of water at 15 ° C. for 3 minutes. The cloudiness was visually observed, and the rinsing property was evaluated based on the following criteria. ◎: No bubbles at all, rinsing water also transparent ○: Very slight bubbles, rinsing water almost transparent △: Some bubbles, rinsing water slightly turbid ×: Many bubbles remaining, rinsing water turbid ing

[Solubility test] Tap water cooled to 5 ° C. was gently stirred with a stirrer, 5 g of a detergent was added thereto, and the mixture was stirred for 8 minutes. Some undissolved particles at 105 ° C
After drying for an hour, the weight of the particles remaining undissolved was weighed, and the residue dissolved was calculated by the following equation. Dissolved residue (%) = ｛weight of undissolved particles (g) / 5
(G)｝ × 100

[Fluidity test] Based on JIS Z2502, each of the detergent particles immediately after production and the detergent particles after storage has a fluidity at room temperature, and the detergent particles immediately after production have been placed in a thermostatic chamber maintained at 45 ° C. for 5 hours. The fluidity after standing was also measured. [Exudation test] After storage under the above conditions, all the detergents were taken out, and the degree of exudation of the inside of the box in contact with the detergent was visually evaluated according to the following criteria. ◎: No exudation was observed. ○: Exudation was slightly observed. Δ: Exudation was observed a little. ×: Exudation was observed. [Solidification test] After storing under the above conditions, the upper part of this container was removed. The sieve was opened, carefully transferred onto a JIS standard 4 mesh sieve, and the sieve was gently vibrated. The weight on the sieve and the total weight were measured, and the solidification property was calculated from the following equation. Solidification (%) = {weight on screen (g) / total weight (g)} × 100

[Bulk density test] The bulk density was measured according to JIS Z2504. [Maskability test] Detergent immediately after production in a container,
The upper part of the container was opened for both the detergent and the detergent stored under the above conditions, and the odor at that moment was organoleptically evaluated based on the following criteria. ◎: No off-flavor at all ○: Slight off-flavor △: Off-flavor ×: Strong off-flavor

Production Example 1 In the table, a nonionic surfactant, an oil-absorbing carrier, bentonite and other optional components (SKS (crystalline layered sodium silicate), soda ash B (light sodium carbonate), PC (sodium percarbonate), Detergent components excluding OBC (decanoyloxybenzene carboxylic acid), PEG (polyethylene glycol), silicone, enzymes, and fragrances were dissolved or dispersed in water to prepare a slurry (water content: 50% by weight). Next, this slurry was sprayed into a spray dryer using a spray nozzle, and the hot air temperature was 240 to 300 ° C.
To obtain dried particles. Next, the dried particles, a nonionic surfactant, an oil-absorbing carrier, bentonite and soda ash B were added to a continuous kneader (KRC-4 manufactured by Kurimoto Tekko Co., Ltd.).
) And kneaded at 40-45 ° C (average residence time:
(20-25 seconds) to produce a solid detergent. This solid detergent was put into a Fitzmill (DKASO6, manufactured by Hosokawa Micron Corp.) together with zeolite A (crystalline sodium aluminosilicate) as a grinding aid, and the average particle size was 400 to 600 μm in the presence of 10 ° C. cold air. The pulverization process was carried out until Finally, zeolite A in the rolling drum
To cover the pulverized particles, and further, SKS, PC, OB
C, PEG, silicone, enzymes, fragrances, and other optional components were added to form detergent particles (average particle size: 450 to 550 μm).
m).

Production Example 2 In the table, nonionic surfactant, oil-absorbing carrier, 12HSA
(12-hydroxystearic acid) and other optional components (S
Detergent components excluding KS, soda ash B, PC, OBC, PEG, silicone, enzyme, and fragrance were dissolved or dispersed in water to prepare a slurry (water content: 50% by weight). Next, the slurry was sprayed into a spray dryer using a spray nozzle, and dried at a hot air temperature of 240 to 300 ° C. to obtain dried particles. Then, the dried particles and a nonionic surfactant, an oil absorbing carrier, 12HSA, SKS and soda ash B
To the Reedige Mixer (Matsubo Co., Ltd., M-20)
), And granulated by stirring at 40 to 45 ° C for 3 minutes. Finally, zeolite A was added in a tumbling drum to coat the obtained detergent particles, and further, PC, OBC, PEG, silicone, enzyme And arbitrary components such as perfume and the like to obtain detergent particles (average particle diameter: 450 to 550 μm).

[Raw Materials Used] The α-sulfofatty acid lower alkyl ester salt, nonionic surfactant, fatty acid soap, oil-absorbing carrier, clay mineral and nonionic gelling agent used in Examples and Comparative Examples are as follows. .

Α-sulfofatty acid lower alkyl ester salt (1) SF-1 sodium α-sulfomyristate methyl ester,
2: 2 (weight ratio) mixture with sodium α-sulfopalmitic acid methyl ester (2) SF-2 sodium α-sulfomyristic acid methyl ester;
α-sulfopalmitic acid methyl ester sodium,
2: 3: 1 (weight ratio) mixture with sodium α-sulfooleic acid methyl ester (3) SF-3 sodium α-sulfomyristate methyl ester;
α-sulfopalmitic acid methyl ester sodium,
α-sulfomyristinic acid methyl ester potassium, α
7 with potassium sulfopalmitic acid methyl ester:
28: 3: 12 (weight ratio) mixture

Nonionic surfactant (1) N-1 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₇ H (Connol 20 manufactured by Shin Nippon Rika Co., Ltd.)
Polyoxyethylene alkyl ether obtained by adding an average of 7 mol of ethylene oxide to P (primary alcohol, carbon number 12, branching degree 0%), manufactured by Lion Chemical Co., Ltd., trade name:
LAG-S) (2) N -2 C 13 H 27 O (CH 2 CH 2 O) 9 H ( Mitsubishi Chemical Corporation Dia manufactured Doll
3 (primary alcohols, 13 carbon atoms, degree of branching 50%) Polyoxyethylene alkyl ethers of ethylene oxide to the average 9 mols) (3) N-3 C 12-13 H 25-27 O (CH 2 CH 2 O) ₇ H (Connol 20P manufactured by Shin Nippon Science Co., Ltd. (primary alcohol, carbon number 12, branching degree 0)
%) And Diadol 13 (primary alcohol, carbon number 13, degree of branching 50%) manufactured by Mitsubishi Chemical Corporation at a weight ratio of 1: 4 and ethylene oxide on average of 7
Mole addition to polyoxyethylene alkyl ethers, Lion Chemical Co., Ltd., trade name: NALG-83) (4) N-4 C 13 H 27 O (CH 2 CH 2 O) 7 (CH 3 CHCH 2) 3 H (Polyoxyethylene polyoxypropylene alkyl ether obtained by adding ethylene oxide on average 7 mol propylene oxide on average 3 mol block to Diadol 13 (primary alcohol, carbon number 13, branching degree 50%) manufactured by Mitsubishi Chemical Corporation) _{5) N-5 C 12-15 H} 25-31 O manufactured by _{(CH 2 CH 2 O) 9} H ( Mitsubishi Chemical Corporation Dobanol 25 (primary alcohols, 12 to 15 carbon atoms, degree of branching 25%) in Polyoxyethylene alkyl ether with an average of 9 moles of ethylene oxide added, Lion Chemical Co., Ltd.
Ltd., trade name: Dobanokkusu 25I) (6) N-6 C 11 H 23 CO (CH 2 CH 2 O) 9 OCH 3 ( Lion oleochemical KK methyl laurate (number of carbon atoms in the fatty acid residues 11) (7) N-7 polyoxyethylene sorbitan monooleate (polyoxyethylene sorbitan fatty acid ester of sorbitan monooleate with an average of 20 moles of ethylene oxide added thereto) , Nikko Chemicals Co., Ltd., TO-10)

Fatty acid soap (1) S-1 sodium palmitate, sodium oleate,
1: 3: 1 of TMD (C10-20 ester compound)
(2) Mixture of S-2 sodium laurate and sodium oleate in a ratio of 1: 1 (weight ratio) (3) S-3 Sodium laurate oil-absorbing carrier (1) K-1 Crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., oil absorption 170 ml / 100 g) (2) K-2 amorphous water-containing amorphous silicic acid (Tokuseal N manufactured by Tokuyama Corporation, oil absorption 280 ml / 100 g) (3) K-3 Petal-like calcium silicate (Flolite R manufactured by Tokuyama Corporation, oil absorption 600ml / 100g)

Clay mineral bentonite: Ca-type bentonite (Mitsubishi Corporation)
BPW009) Nonionic gelling agent 12HSA: 12-hydroxystearic acid (KF Trading Co., Ltd.)

[0047]

Table 1 Example Granular Nonionic Detergent Composition 1 2 3 4 5 6 Composition (% by weight) α-Sulfo fatty acid lower alkyl ester salt (a) SF-1 17 10 8 6 28 32 Nonionic surfactant (b) ) N-3 20 22.4 25 27 8.4 11.7 N-7 0.4 0.6 1 2 0.1 0.3 Fatty acid soap (c) S-1 8.7 3.2 2.2 5.5 20 19 (a) / (b) 0.8 0.4 0.3 0.2 3.3 2.7 (a) / (C) 2.0 3.1 3.6 1.1 1.4 1.7 Oil-absorbing carrier K-1 7 8 9 12 2 4 K-22 2--1- K-3 21 46-2 Optional component LAS-Na 0.1---0.1- LAS-K 0.3 0.2 0.5 0.1 0.4-AOS-Na-0.1--0.1-AOS-K 0.1 0.1 0.3 0.1 0.2-Zeolite A 8 9 15 13 6 8 SKS 5 3 7 5 12 5 sulfite 1.5 3 1 0.5 2 1 Soda ash A 13 15 7 4 9 7 Bentonite 4 4 6 6 2 3 Sodium percarbonate (PC)-32---OBC-1.5----MA 55 56 72 3 PAS 0.1 0.2 0.2 0.2 0.1 0.1 PEG-0.5-0.8--Silicone 0.1 0.3 0.05 0.01 0.2 0.1 Fluorescent agent A 0.2 0.3 0.1 0.1 0.2 0.2 Fluorescent agent B 0.1 0.2 0.1-0.2-Enzyme A 1 1.5 1 0.5 21 Enzyme B 0.5 1--1- Fragrance 0.25 0.25 0.25 0.25 0.25 0.25 Other minor components Bla * Bla Bla Bla Bla Bla manufacturing method 1 1 1 1 1 1 Evaluation results Detergency test Immediately after production Cotton 82 81 79 76 84 85 Acrylic 82 83 84 85 75 79 Nylon 82 83 84 85 76 79 After storage Cotton 81 80 78 75 80 83 Acrylic 82 83 83 82 75 79 Nylon 82 83 83 81 76 79 SF hydrolysis increase 2 2 2 2 8 5 Residual residue (%) 1 0.5 2 5 8 8 Rinseability ◎ ◎ ○ ◎ ◎ ◎ Fluidity (°) Immediately after production 40 40 40 40 40 40 40 After storage 40 40 42 45 45 43 45 ° C 40 40 42 45 45 43 Exudation ◎ ◎ ◎ ○ ◎ ◎ Solidification (%) 0 0 3 5 5 4 Bulk density (g / cm ³ ) 0.80 0.84 0.83 0.84 0.70 0.70 Masking Immediately after production ◎ ◎ ○ ○ ◎ ◎ After storage ◎ ◎ ○ ○ ◎ ◎ No stickiness None None None None None No adhesion to equipment None None None None None *) Represents

[0048]

Table 1 (Continued) Example Granular Nonionic Detergent Composition 7 8 9 10 11 12 Composition (% by weight) α-Sulfo fatty acid lower alkyl ester salt (a) SF-1 38--10--SF-2 -10--10-SF- 3--10--10 Nonionic surfactant (b) N-1 ---- 18-N-2-18----N-3 15.5-----N -4-----17 N-5---18--N-6--18---N-7 0.5 ---- 1 Fatty acid soap (c) S-1 9.7--5--S -2-5--5 -S- 3--5--5 (a) / (b) 2.4 0.6 0.6 0.6 0.6 0.6 (a) / (c) 3.9 2.0 2.0 2.0 2.0 2.0 Oil-absorbing carrier K-19 11 3 13 11 - K-2 - - 2 - 2 3 K-3 1 - 2 3 - - optional components LAS-Na - 0.5 - - - 0.2 LAS-K 0.1 - - - 1 0.3 AOS-Na - - - - -0.1 AOS-K-----0.1 Zeolite A 9 10 11 8 14 25 SKS 3 23 12 16 8 3 Sulfite 1 1 1 1 1.5 2 Soda ash A 4-22 7 8 16 Soda ash B-2 --7-12HSA-3-5 4 3 Sodium percarbonate-3---5 OBC-1---1 MA 4 2 5 7 3 2 PAS 0.1 1 0.2--0.1 PEG-0.5---0.3 Silicone 0.01 0.01-0.1 0.2-Fluorescent agent A 0.1 0.3 0.2 0.2 0.2 0.2 Fluorescent agent B 0.1 0.1-0.1 0.2-Enzyme A 0.1 1 1.5 0.5 1 1 Enzyme B 0.2 1-0.5 0.5 0.5 Fragrance 0.25 0.2 0.1 0.2 0.2 0.2 Other minor components Bla * Bla Bla Bla Bla Bla manufacturing method 1 2 2 2 2 2 Evaluation result Detergency test Immediately after production Cotton 85 81 81 81 81 81 Acrylic 82 81 81 81 81 81 Nylon 82 81 81 81 81 81 Cotton 84 81 81 81 81 after storage 80 Acrylic 82 81 81 81 81 81 Nylon 82 81 81 81 81 81 SF hydrolysis increase rate 2 1 0 0 0 2 Dissolution residue (%) 6 0.5 0 1 0 1 Rinseability ◎ ◎ ◎ ◎ ◎ ◎ Fluidity (° ) Immediately after production 40 40 40 40 40 40 After storage 45 40 45 40 40 40 45 ° C. 48 40 48 40 40 40 Exudation ◎ ◎ ○ ◎ ◎ ◎ Solidification (%) 5 0 3 0 0 0 Bulk density (g / cm) ³⁾ 0.73 0.82 0.88 0.85 0.83 0.82 masking made Immediately after ○ ◎ ◎ ◎ ◎ ◎ after the storage ○ ◎ ◎ ◎ ◎ ○ sticky adhesion state Mu NO NO NO NO only to the extent Mu NO NO NO NO only apparatus of the Note) * Bla represents the remaining amount

[0049]

Table 1 (Continued) Comparative Example Granular Nonionic Detergent Composition 1 2 3 4 5 5 α-Sulfo fatty acid lower alkyl ester salt (a) SF-3 3 4 2 8 2 1 1 10 Nonionic surfactant N-6 32 5 5 18. 18 fatty acid soap S-3 5 122 5 55 (a) / (b) 0.1 8.4 3.6 1.2 0.6 (a) / (c) 0.6 42 0.8 4. 2 2.0 oil-absorbent carrier K-1 10 5 1 8 - K-3 4 4 - 4 - optional component zeolite A 10 10 10 10 11 SKS 5 5 5 5 12 nitrous硫曹1 1 1 1 1 soda ash A 17 15 26 16 29 MA 55 55 55 PAS 0.2 0.2 0.2 0.2 0.2 Fluorescent agent A 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme A 1.5 1 .5 1.5 1.5 1.5 perfume 0.2 0.2 0.2 0.2 0.2 other minor growth Bla Bla Bla Bla Bla Process 1 1 1 1 2 Evaluation Results detergency test preparation immediately after cotton 68 84 82 83 81 Acrylic 85 68 68 81 81 nylon 85 67 67 81 81 after storage cotton 63 70 72 80 81 nylon 75 67 67 71 81 SF hydrolysis increase rate 2 28 20 2 ○ Dissolution residue (%) 20 29 40 16 ○ Rinseability ◎ × ◎ ◎ ◎ Flowability (°) Immediately after production 40 40 40 40 45 After storage 80 90 85 60 65 45 ° C. 90 90 90 90 90 exudation × ◎ ◎ × × solidifying (%) 30 45 40 40 30 bulk density ^{(g / cm 3) 0.83 0.80} 0.80 0.81 0.83 masking immediately after production × × ◎ × ◎ After storage × × △ × × No stickiness No No No No Adhesion to very large equipment No No Many No The raw materials used in are as follows. LAS-Na: straight-chain C11-13 sodium alkylbenzenesulfonate LAS-K: straight-chain C11-13 potassium alkylbenzenesulfonate AOS-Na: C14-16 sodium α-olefin sulfonate AOS-K: C14-16 Potassium α-olefin sulfonate AS-Na: sodium lauryl sulfate zeolite A: crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd.) SKS: crystalline layered sodium silicate (manufactured by Hoechst Japan, SKS-6) sulfite: sulfurous acid Sodium (manufactured by Shinshu Chemical Co., Ltd., anhydrous sodium sulfite) Soda ash A: heavy sodium carbonate (manufactured by Asahi Glass Co., Ltd., grain ash) Soda ash B: light sodium carbonate (manufactured by Asahi Glass Co., light ash) Sodium: PC particles manufactured by Mitsubishi Gas Chemical Company, Inc. OBC: Decanoyloxybenzenecarboxylic acid (Mitsui Toatsu) MA: 7/3 copolymer of acrylic acid and maleic acid (manufactured by BASF, Sokaran CP5) PAS: Sodium polyacrylate (manufactured by Nippon Pure Chemical Co., Ltd., Rheogic 250H) PEG : Polyethylene glycol (manufactured by Lion Chemical Co., Ltd., PEG6000) Silicone: silicone compound (manufactured by Dow Corning, FS antiform) Fluorescent agent A: 2: 4,4'-bis (2-sulfostyryl) biphenyl disodium (Ciba-Geigy, Tinopearl CBS-X) Fluorescent agent B: 1: 4,4'-bis (4-amino-6-morpholino-1,3,5-triazinylamino) stilbene disulfonic acid (manufactured by Sumitomo Chemical Co., Ltd.) (Whitetex SA) Enzyme A: 7/2 of alkali protease granules and alkali lipase granules (weight ratio) A mixture of (Novo Nordisk, a mixture of Savinase 12T / Lipolase EX = 7/2) Enzyme B: alkaline protease granules (Novo Nordisk, Deyurazaimu 8T) Perfume: see below perfume composition parts 3,7-dimethyl -1,6-octadien-3-ol 80 3,7-dimethyl-1,6-octadien-3-yl-acetate 60 3,7-dimethyl-6-octen-1-ol 40 β-phenylethyl alcohol 50 p -Tert-butyl-α-methylhydrocinnamic aldehyde 70 α-methyl-p-isopropylphenylpropionaldehyde 60 α-n-amylcinnamic aldehyde 20 α-n-hexylcinnamic aldehyde 607-acetyl-1,1,3, 4,4,6-hexamethyltetrahydronaph Len 80 3- (5,5,6-trimethyl-norbalnan-2-yl) cyclohexane-1-ol 20 Beltfix 30 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl ) -2-butan-1-ol 10% 10 α, α-dimethyl-p-ethylhydrocinnamic aldehyde 40 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde 10 cis-3-hexenol 10 2-trans -3,7-dimethyl-2,6-octadien-1-ol 30 n-decylaldehyde 5 10-undecene-1-al 5 methylnonylacetaldehyde 5 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene -1-Carboxaldehyde 30 naphthalene-2-acetyl-1,2,3 , 4,6,7,8-Octahydro2,3,8,8-tetramethyl 30 5- (2-methylene-6,6-dimethyl-cyclohexyl) -4-penten-3-one 50 2-methoxy-4 -Propenylphenol 20 allylcyclohexanepropionate 10 6,7-dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanone 5 p-propenylphenyl methyl ether 5 methyl-2-aminobenzoate 5 lemon Oil 30 Orange oil 20 Lavandin oil 20 Patchouli oil 10 3,7-Dimethyl-2,6-octadienal 30 Methyldihydrojasmonate 50 Percentage of fragrance components having a boiling point of 230 ° C. (1 atm) in all fragrances ( wt%) was 66%.

[0050]

According to the present invention, α-sulfo fatty acid lower alkyl ester salt, nonionic surfactant and fatty acid soap are blended in a specific amount and a specific ratio,
It has a multifunctional detergency regardless of the type of cloth to be washed and stains, has good rinsing properties, has excellent storage stability, has little unpleasant odor, is easy to mask, and has good biodegradability. Thus, it is possible to provide a granular detergent composition that can be produced more stably.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 9:00 3:02)

Claims (2)

[Claims] 1. The following components: (a) α-sulfo fatty acid lower alkyl ester salt: 5 to 5
A particulate detergent composition comprising: 40% by weight; (b) a nonionic surfactant: 7 to 30% by weight; (c) a fatty acid soap: 2 to 20% by weight; and (d) an oil-absorbing carrier. a) / (b) (weight ratio) = 0.2-3.5, and (a) / (c) (weight ratio) = 1.0-4.0 Detergent composition. 2. The granular detergent composition according to claim 1, further comprising a clay mineral and / or a nonionic gelling agent.