JPH1135980A - Granulated nonionic detergent composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound containing an organic builder having a good biodegradability by blending a nonionic surfactant, a clay mineral, and an iminocarboxylic acid or its salt to improve the flowability and cakability of the detergent particles at a high temperature. SOLUTION: A nonionic detergent compound contains 15-40 wt.% of a nonionic surfactant having a melting point not more than 40 deg.C and an HLB of 9-16, 0.1-30 wt.% of a clay mineral which belongs to a smectite group, has a crystalline structure of a dioctahedral type three-layer structure or a trioctahedral type three-layer structure and exhibits an oil absorption of less than 80 ml/100 g, 0.5-30 wt.% of an iminocarboxylic acid or its salt of formula I or II (wherein R is H or a hydroxide group and X is H, an alkali metal or an ammonium group) and various optional components which are usually blended for a raw material for a detergent if necessary. The nonionic detergent compound is obtained by mixing granulation of this compound or by crushing granulation after kneading extrusion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granular nonionic detergent composition containing an organic builder having improved biodegradability and improved fluidity and solidification of detergent particles at high temperatures.

[0002]

2. Description of the Related Art Conventionally, various surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants have been used in detergent compositions. Of these, nonionic surfactants are generally
It has low foam, and its detergency is less affected by water hardness.
In particular, it is excellent in mud dirt and dispersibility of dirt at low temperatures. Further, nonionic surfactants are excellent surfactants having good biodegradability, low environmental load, low toxicity and high 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 the product appearance deteriorates, but also the nonionic surfactant decreases at the container contact portion, thereby deteriorating the detergency and further improving the fluidity and caking resistance of the detergent particles. Sex is adversely affected. In addition, since nonionic surfactants are weak to heat, the conventional method of spray-drying a mixed slurry of surfactant and cleaning builder causes the nonionic surfactant to thermally decompose. It is not preferable because it is released to the atmosphere as exhaust gas, which may cause environmental destruction such as air pollution.

On the other hand, in recent years, there has been an increasing demand for environmentally friendly detergents. For example, builders that do not cause eutrophication in lakes and marshes are being developed. For example,
JP-A-5-170714, JP-A-6-248300 and JP-A-8-311494 disclose an iminocarboxylic acid or a salt thereof produced by reacting maleic acid or its epoxidized product with aspartic acid. A cleaning builder having excellent decomposability is disclosed. However, when an organic builder excellent in biodegradability is added to a granular nonionic detergent composition containing a particularly large amount of a nonionic surfactant, unexpectedly, the flowability of the detergent particles at high temperatures is reduced. It was also found that the solidification property was reduced.

[0004]

Accordingly, the present invention provides a granular nonionic detergent composition containing an organic builder having improved biodegradability and improved fluidity and solidification of detergent particles at high temperatures. The purpose is to:

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a granular nonionic detergent composition containing an organic builder having excellent biodegradability is provided.
The present inventors have found that the above problems can be effectively solved by blending a clay mineral, and have reached the present invention. That is, the present invention relates to the following inventions. 1. Nonionic surfactant, clay mineral, and the following general formula
A granular nonionic detergent composition comprising the iminocarboxylic acid represented by (I) or (II) or a salt thereof.

[0006]

Embedded image (In the formula, R is a hydrogen atom or a hydroxyl group, and X is a hydrogen atom, an alkali metal or an ammonium group.) 2. Nonionic surfactant, clay mineral, and the following general formula
A method for producing a granular nonionic detergent composition, comprising subjecting the iminocarboxylic acid or a salt thereof represented by (I) or (II) to stirring granulation, or kneading and extruding, followed by crushing and granulation.

[0007]

Embedded image (In the formula, R is a hydrogen atom or a hydroxyl group, and X is a hydrogen atom, an alkali metal or an ammonium group.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The nonionic surfactant used in the present invention is not particularly limited as long as it can be conventionally used for detergents, and various nonionic surfactants can be used. Preferred nonionic surfactants include:
For example, the following can be mentioned. (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. (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 2 to 4 carbon atoms such as ethylene oxide and propylene oxide. Represents an addition unit of alkylene oxide, preferably 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 1 to 3 substituents. (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.

Among the above-mentioned nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers and polyoxyethylene polyoxypropylene alkyl (or alkenyl) having a melting point of 40 ° C. or less and an HLB of 9 to 16, especially 9 to 15, are used. Particularly preferred are fatty acid methyl ester ethoxylate in which ethylene oxide is added to ether and fatty acid methyl ester, and fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to fatty acid methyl ester.
Further, these nonionic surfactants may be used as a mixture. The nonionic surfactant is contained in the granular nonionic detergent composition preferably at 15 to 40% by weight, more preferably 18 to 35% by weight, particularly preferably 20 to 30% by weight. If the amount is less than 15% by weight, not only the concentration of the nonionic surfactant in the obtained detergent is low, but also if the amount of the detergent is not increased, a good cleaning effect cannot be obtained, which is not preferable. On the other hand, if the amount exceeds 40% by weight, a problem of adhesion to the device during the production of the detergent tends to occur, which is not preferable.

As the clay mineral used in the present invention, in particular, those belonging to the smectite group and having a three-layered dioctahedral or trioctahedral crystal structure can be preferably used. Such a clay mineral has a cleavage property and has a layered structure. This clay mineral has a property of chemically adsorbing a nonionic surfactant between its crystal layers by hydrogen bonding and retaining it inside the clay mineral. Note that the clay mineral has a smaller oil absorption amount than the arbitrarily used oil-absorbing carrier described below. The clay mineral has a property of swelling as the nonionic surfactant is retained inside. The clay mineral preferably used in the present invention preferably has an oil absorption of 80 ml.
/ 100g, more preferably 30-70ml / 10
0 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. As a clay mineral having a trioctahedral type three-layer structure, saponite (oil absorption: 73 ml / 100
g), hectorite (oil absorption: 72 ml / 100 g),
Stephensite (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. Such clay minerals are 10-
As long as a peak derived from the spread of the clay layer detected at 20 ° and a peak derived from the three-layered structure of clay detected at 4 to 5 ° are developed, they can be used without particular limitation. In addition, clay minerals, particularly 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 at least a purity of at least. It is preferable to use 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 clay mineral is contained in the high bulk density granular nonionic detergent composition preferably in an amount of 0.1 to 30% by weight, more preferably 1 to 20% by weight, and particularly preferably 3 to 10% by weight. If this amount is less than 0.1% by weight, the flowability and solidification of the resulting detergent particles at high temperatures tend to be significantly reduced. On the other hand, if the content exceeds 30% by weight, the obtained detergent particles become too hydrophobic, so that the solubility of the detergent tends to deteriorate, which is not preferable. The oil-absorbing carrier arbitrarily used in the present invention is preferable because it further suppresses exudation of the nonionic surfactant and solidification of the detergent particles at a high temperature, and further improves the solubility of the detergent when the detergent is used. is there. The oil-absorbing carrier is a porous fine powder sufficient to adsorb and retain the nonionic surfactant, and physically adsorbs the nonionic surfactant, but does not swell due to this. The oil absorption of the oil-absorbing carrier used in the present invention is larger than that of the clay mineral. Preferred oil-absorbing carriers include JIS-K
The oil absorption expressed by the 5101 test method is 80 ml / 100
g or more, preferably 150 to 600 ml / 100 g of an oil-absorbing substance is suitably used. As such an oil-absorbing carrier, for example, as a silicate compound, Tokusil N (manufactured by Tokuyama Corporation, oil absorption amount 280 ml / 100)
g), Nip Seal NS-K (Nippon Silica Co., Ltd., oil absorption 320 ml / 100 g), Thylsia # 310 (Fuji Silysia Chemical Co., Ltd., oil absorption 340 ml / 100 g)
Such as amorphous hydrous amorphous silicic acid, Sildex H-52
Aerosil # 300 (manufactured by Asahi Glass Co., Ltd., oil absorption amount 260 ml / 100 g), etc., Aerosil # 300 (Nippon Aerosil Co., Ltd., oil absorption amount 350 ml / 100 g)
Such as amorphous anhydrous silicic acid, Florite R (Co., Ltd.)
Petal-like hydrous amorphous calcium silicate such as Tokuyama, oil absorption 600ml / 100g), acicular hydrous crystalline calcium silicate such as zonotlite (oil absorption 220ml / 100g, manufactured by Ube Chemical Co., Ltd.), amorphous aluminosilicate Salt (manufactured by Mizusawa Chemical Co., Ltd., oil absorption 170 ml / 100 g), magnesium silicate (oil absorption 180 ml / 100 g), and the like. Further, as a carbonate compound, magnesium carbonate (manufactured by Tokuyama Corporation, oil absorption 150 ml / 100 g),
Calcium carbonate (Shiraishi Industry Co., Ltd., oil absorption 110ml
/ 100 g), and ultrafine spinel (manufactured by Sumitomo Cement Co., Ltd., oil absorption 600 ml / 100
g), ultra-fine particle cordierite (Sumitomo Cement Co., Ltd.)
Oil absorption 600ml / 100g), ultrafine mullite (Sumitomo Cement Co., Ltd., oil absorption 560ml / 100)
g), processed starch pine flow S (manufactured by Matsutani Chemical Co., Ltd., oil absorption amount 130 ml / 100 g) and the like. These oil absorbing carriers may be used as a mixture.

The oil-absorbing carrier is preferably present in the granular nonionic detergent composition in an amount of 0.1 to 20% by weight, more preferably 0.5%.
-15% by weight, particularly preferably 1-10% by weight. If the amount is less than 0.1% by weight, the nonionic surfactant is likely to exude, and the resulting detergent particles are likely to deteriorate in fluidity and solidification at high temperatures. On the other hand, even if this amount exceeds 30% by weight, a drastic improvement in the accompanying effect cannot be expected. The iminocarboxylic acid or a salt thereof used in the present invention is a compound represented by the following formula (I) or (II).

[0015]

Embedded image (In the formula, R is a hydrogen atom or a hydroxyl group, and X is a hydrogen atom, an alkali metal or an ammonium group.) The iminocarboxylic acid represented by the above formula (I) is already known, for example, It can be produced, for example, by reacting maleic acid or epoxy succinic acid with aspartic acid according to the method described in JP-A-5-17714. In particular, by reacting epoxysuccinic acid and aspartic acid, a hydroxyiminocarboxylic acid in which R in the above formula is a hydroxyl group is produced. Further, the iminocarboxylic acid represented by the above formula (II) is
According to the above reaction, maleic acid or epoxy succinic acid,
It can be produced by reacting with glycine.

[0016] The iminocarboxylic acid can also be used as a salt. Examples of the salt of an iminocarboxylic acid include alkali metal or ammonium salts. Examples of the alkali metal include sodium, lithium, potassium and the like. Preferred salts include, for example, alkali metal salts, particularly, sodium salts and potassium salts. Further, the iminocarboxylic acid may be partially neutralized. The iminocarboxylic acid or a salt thereof may be used as a mixture. In the present invention,
The iminocarboxylic acid or a salt thereof is suitably used in an amount of preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight, based on the weight of the granular nonionic detergent composition. 0.5% by weight of iminocarboxylic acid or its salt
If the amount is smaller than the above range, the cleaning power of the detergent tends to decrease. On the other hand, if the amount of iminocarboxylic acid or its salt exceeds 30% by weight, the solubility of the detergent composition tends to deteriorate.

In the granular nonionic detergent composition of the present invention,
As long as it is an optional component usually blended in a detergent raw material, various components can be used in combination without any particular limitation. Examples of such components include the following 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 a chelate builder, sodium aluminosilicate, potassium aluminosilicate, sodium tripolyphosphate, sodium pyrophosphate, NTA, EDTA and the like. (3) As anionic surfactants, linear alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfates, alkyl ether sulfates and the like. (4) As a fluorescent agent, for example, bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X] and the like. (5) Examples of enzymes include lipase, protease, cellulase, amylase and the like. (6) Bleaching agents such as percarbonates and perborates. (7) Examples of the bleach activator include sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzenecarboxylic acid, and the like. (8) Examples of the surface modifier include fine calcium carbonate, fine zeolite, fine silica, fine alumina, finely modified starch, bentonite, and polyethylene glycol. (9) Polyalkylene glycol, sodium carboxymethylcellulose, polyvinyl alcohol, and the like as a re-staining agent. (10) As a bulking agent, for example, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like. (11) As a reducing agent, for example, sodium sulfite,
Potassium sulfite and the like. (12) As a foam inhibitor, for example, silicone oil,
Silicone compounds, etc. (13) Fragrances (14) Dyes These optional components can be blended into the granular nonionic 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.

The granular nonionic detergent composition of the present invention can be produced, for example, by stirring granulation by stirring granulation, or by crushing granulation after mixed extrusion. In stirring granulation, a nonionic surfactant and an iminocarboxylic acid or a salt thereof are added at the time of stirring granulation, and the mixture is uniformly granulated. At this time, other detergent components, for example, zeolite, sodium carbonate, a fluorescent agent and the like may be added. Various modifications are conceivable in producing the granular nonionic detergent composition of the present invention. For example, a nonionic surfactant, a clay mineral, an optional oil-absorbing carrier, (partly) zeolite,
After forming a slurry of the components excluding enzymes, fragrances, etc., and spray-drying, dry powder and components such as a nonionic surfactant, a clay mineral, an oil-absorbing carrier are added to a stirring granulator, and the mixture is stirred and granulated. . The slurry concentration is, for example, 40 to 60% by weight,
Preferably, the content is 45 to 55% by weight.

As the stirring granulator used in the stirring granulation operation, a stirring blade is provided inside a granulator such as a high-speed mixer, a sugar mixer, a Loedige mixer, etc. An internal stirring type granulator having a clearance of 30 mm or less is preferably used to obtain high bulk density detergent particles. The temperature of the stirring granulation is generally 20
-60 ° C, preferably 30-50 ° C, more preferably 3 ° C
5-50 ° C. If the temperature is lower than 20 ° C,
Granulation does not easily proceed, which is not preferable. On the other hand, if the temperature is higher than 60 ° C., on the other hand, the adhesion in the granulator increases, and the load tends to be excessive, which is not preferable. Further, the processing time in the stirring granulation processing is usually 1 to 10 minutes, preferably 2 minutes.
~ 8 minutes. On the other hand, the nonionic detergent composition of the present invention comprises:
As in the case of the stirring granulation described above, the mixture is introduced into a kneading extruder, preferably a closed-type compacting apparatus, more preferably a horizontal continuous kneader, and mixed while applying a shearing force in the kneader. The nonionic detergent composition of the present invention can be produced by forming granules (solid detergent), then crushing and granulating with a crushing granulator, and performing compaction treatment. In this case, in addition to the kneader, a single-screw or twin-screw extruder can be used. Specific examples of the kneading extruder used in the present invention include a KRC kneader manufactured by Kurimoto Ironworks Co., Ltd. As the crushing granulator, a cutter mill or the like can be used. As the crushing granulator, for example, Fitzmill (DKASO6) manufactured by Hosokawa Micron Corporation or the like can be used. The temperature of the kneading extruder is generally 30 to 60 ° C, preferably 35 to 55 ° C, more preferably 40 to 50 ° C. If the temperature is lower than 30 ° C., the load on the kneading extruder tends to be excessive, which is not preferable. On the other hand, when the temperature is higher than 60 ° C,
The kneaded material tends to adhere to the pulverizer, which is not preferable. The processing time is usually 0.2 to 2 minutes, preferably 0.5 to 1 minute. The crushing and granulation treatment is generally performed at 5 to 30C, preferably 10 to 25C, and more preferably 10 to 20C. If the temperature is lower than 5 ° C., dew condensation easily occurs, which is not preferable. On the other hand, if the temperature is higher than 30 ° C., on the other hand, adhesion to the pulverizer tends to occur, which is not preferable. The processing time is usually 1 to 30 seconds, preferably 3 to 3 seconds.
0 seconds.

According to the present invention, the bulk density is 0.5 to 1.2 g / ml, preferably 0.5 to 1.2 g / ml.
It is preferred to obtain 0.6-1 g / ml compact. Furthermore,
A coating treatment may be added to the thus produced detergent particles to carry out a coating treatment. Thereby, the flow characteristics can be improved. As the coating agent, an inorganic powder having a JIS 200 mesh sieve passing content of 50% or more is suitable. For example, carbonates such as sodium carbonate and calcium carbonate, amorphous silica, calcium silicate, and silicate Silicates such as magnesium and aluminosilicates such as zeolite can be used. The coating agent is generally present in the granular nonionic detergent composition of the present invention in an amount of 0.5 to 15% by weight, preferably 1 to 15% by weight.
It is used in an amount of from 10 to 10% by weight.

Further, an enzyme, a fragrance and the like can be added to the detergent particles thus produced. The obtained granular nonionic detergent composition of the present invention generally has an average particle size of
It is obtained from 300 to 3000 .mu.m, preferably from 350 to 2000 .mu.m, particularly preferably from 400 to 1000 .mu.m.

[0022]

The present invention will be described below in more detail with reference to examples and comparative examples. In the examples and comparative examples, each sample was evaluated by the following test methods. [Bleeding test] Coated cardboard from outside (basis weight: 350
g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² )
A box measuring 15 cm long × 9.3 cm wide × 18.5 cm high was prepared. Place 1.2 kg of the sample in this box, store it in a constant temperature and humidity room at 50 ° C and 85% RH for 30 days, remove all the detergent, and visually check the degree of oozing of the contact area with the detergent inside the box. The evaluation was based on the following criteria. ：: No exudation was observed. ○: Exudation was slightly observed. Δ: Exudation was observed a little. ×: Exudation was observed much. [Solidability test] Coated cardboard from outside (basis weight: 350 g) /
m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) using three layers of paper, length 15 cm × width 9.3 cm × height 18.5 cm boxes were made. Put 1.2 kg of sample in this box and place it in a 50 ° C, 85% RH constant temperature and humidity room.
After storage for 30 days, the detergent was 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 determined, and the solidification property was evaluated from the following equation 1. Formula 1: solidification (%) = {weight on sieve (g) / total weight (g)} × 100

[Solubility Test] Tap water at 5 ° C. was put into a 500 ml beaker, 5 g of the detergent composition was added, and the mixture was stirred for 5 minutes. Next, the detergent particles remaining undissolved were taken out on a nylon cloth, dried at 105 ° C. for 2 hours, and a dissolved residue represented by the following formula 2 was calculated and evaluated according to the following criteria. Formula 2: dissolution residue (%) = {(dissolution residue at 105 ° C. for 2 hours, dried product (g) / 5g)} × 100 ◎: 0% ≦ dissolution residue <1% ○: 1% ≦ dissolution residue <5% Δ: 5% ≦ dissolution residue <10% X: 10% ≦ dissolution residue [Fluidity test] 45 ° C. based on JIS Z2502
The angle of repose at was measured by the discharge method. [Bulk density] The bulk density was measured according to JIS Z2504. [Attachment Test to Granulator] After discharging the granulated detergent particles, the granulator was opened, and the amount of the detergent adhered to the inner side wall and the stirring blade was visually evaluated according to the following criteria. No: Not attached at all Slight: Thin and slightly attached Many: A large amount adhered [detergency test]

(1) Preparation of Artificial Soil A clay mainly composed of crystalline minerals such as kaolinite and vermiculite was dried at 200 ° C. for 30 hours and used as inorganic soil. 3.5g gelatin in 950cc water
After dissolving at 40 ° C., 0.25 g of carbon black was dispersed in water using a powerful emulsifying and dispersing machine, Polytron (Kinematica, Switzerland). Next, 14.9 g of inorganic soil was added and emulsified with Polytron, and 31.35 g of organic soil was further added and emulsified and dispersed with Polytron to form a stable soil bath. A predetermined cleaning cloth (cotton cloth No. 60 designated by the Japan Oil Chemistry Association) of 10 cm × 20 cm was immersed in the dirt bath, and water was squeezed with two rubber rolls to uniform the amount of dirt deposited. This dirty cloth 1
After drying at 05 ° C for 30 minutes, both sides of the soiled cloth were rubbed two times on each side. This is cut into 5cm x 5cm and the reflectance is 42
Those having a range of ± 2% were applied to a soil cloth. The soil composition of the artificial soil cloth thus obtained is shown in Table 1.

[0025]

Table 1 Soil component composition (% by weight) Organic soil: oleic acid 28.3 triolein 15.6 cholesterol oleate 12.2 liquid paraffin 2.5 squalene 2.5 cholesterol 1.6 total oily soil 62.7 Gelatin 7.0 Inorganic 29.8 Carbon Black (Designated by Japan Oil Chemicals Association) 0.5

(2) Washing method Using a Terg-O-Tometer from USTesting, put 10 artificially soiled cloths and a knitted cloth, adjust the bath ratio to 30 times, and wash at 120 rpm, 25 ° C. for 12 minutes. did. Use 900 ml of cleaning solution with a detergent concentration of 0.083%, and rinse with 900 ml of water.
Minutes. The water used was 3 ° DH. (3) Evaluation method The cleaning rate was calculated by the following equation 3. Cleaning rate (%) = (K / S of dirty cloth-K / S of cleaning cloth) / (K / S of dirty cloth-K / S of unsoiled cloth) x 100 K / S = (1- R / 100) ² / (2R / 100) (Kuberka-Munk equation) where R is a reflectance measured by an ELREPHO reflectometer manufactured by Carl Twice. The evaluation of the detergency was carried out by the average value of 10 test artificial soil cloths.

[Production Example A] Of the components shown in Table 2, components other than the nonionic surfactant, clay mineral, oil-absorbing carrier, enzymes, fragrances and some zeolites were slurried under a water content of 50% by weight. Spray-dried to a dry base powder. Next, the dried base powder, the clay mineral and the oil-absorbing carrier were put into a Lodige mixer (M-20, manufactured by Matsubo Co., Ltd.), and the main shaft (200 rpm) and chopper (6000 rpm) were used.
The mixture was uniformly mixed under the stirring of m). Then press the nonionic surfactant into the pressure nozzle (Mike Ikeuchi 120, spray pressure 5kg / cm ² )
And granulation treatment was performed until the average particle diameter became 500 μm. Finally, the remaining zeolite is added in the tumbling drum to coat the particles obtained by stirring granulation,
Further, an enzyme and a fragrance were added to obtain a granular nonionic detergent composition having the properties shown in Table 2 (average particle diameter: 500 μm). [Production Example B] Among the components shown in Table 2, components other than nonionic surfactants, clay minerals, oil-absorbing carriers, enzymes, fragrances, and some zeolites were slurried under a water content of 50% by weight, and spray-dried. It was a dry base powder. Next, the dried base powder, the nonionic surfactant, the clay mineral, and the oil-absorbing carrier were charged into a continuous kneader (KRC-4, manufactured by Kurimoto Tekko Co., Ltd.) and uniformly kneaded to prepare a solid detergent. Further, the solid detergent is crushed and granulated in the presence of zeolite as a grinding aid (Fitzmill DKA, manufactured by Hosokawa Micron Corporation).
(SO-6 type), and crushed and granulated until the average particle diameter became 500 μm. Finally, the remaining zeolite is added in a tumbling drum, and the particles obtained by granulation are coated. Further, an enzyme and a fragrance are added, and a granular nonionic detergent composition having the properties shown in Table 2 (average particle diameter: 500 μm) I got

[Raw Materials] Nonionic Surfactant (1) N-AC ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₇ H (Polypropylene obtained by adding an average of 7 moles of ethylene oxide to Connol 20P manufactured by Shin Nihon Rika Co., Ltd.) polyoxyethylene lauryl ether) (2) N-B C 13 H 27 O (CH 2 CH 2 O) 7 (CH 2 CH (CH 3)
O) ₃ H (polyoxyethylene polyoxypropylene alkyl ether obtained by block addition polymerization of diadol manufactured by Mitsubishi Chemical Corporation with an average of 7 mol of ethylene oxide and an average of 3 mol of propylene oxide) (3) N—C C ₁₁ H ₂₃ CO (CH ₂ CH ₂ O) ₉ OCH ₃ (Lion Oleo Chemical Co., Ltd., methyl laurate added with an average of 9 mol of ethylene oxide to methyl laurate methyl ethoxylate) (4) N-D C ₁₁ H ₂₃ CO (CH ₂ CH) (CH ₃ ) O) ₂ (CH ₂ CH ₂
O) ₉ OCH ₃ (Methyl ethoxypropoxylate laurate obtained by block addition polymerization of propylene oxide on average 2 mol and ethylene oxide on average 9 mol) produced by Lion Oleo Chemical Co., Ltd. clay mineral (1) MA Ca type Montmorillonite (BPW00 manufactured by Meiwa Sangyo Co., Ltd.)
9) (2) MB Na-type montmorillonite (Wenger 2 manufactured by Toyshun Yoko Co., Ltd.)
3) Iminocarboxylic acid (salt) (1) IA Hydroxyiminodisuccinate tetrasodium represented by the following formula (III) (HIDS, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)
(Solid content 40% by weight))

[0029]

Embedded image (2) IB Iminocarboxylate represented by the following formula (IV)

[0030]

Embedded image This iminocarboxylic acid was synthesized as follows. [Synthesis example of iminocarboxylic acid] To a solution obtained by adding 37.5 g of glycine to 500 ml of a 1 mol / liter aqueous solution of maleic anhydride, 55.5 g of calcium hydroxide was gradually added under cooling, and the mixture was refluxed for 10 hours. After the completion of the reaction, 84.8 g of sodium carbonate was added, and the mixture was stirred while heating at 60 ° C., and the precipitated calcium carbonate was filtered. From the obtained filtrate,
The iminocarboxylic acid salt was crystallized from methanol and dried under vacuum to obtain an iminocarboxylic acid powder. Oil-absorbing carrier (1) TA amorphous silica (Sylysia 3 manufactured by Fuji Silysia Chemical Ltd.)
10) (2) TB amorphous aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd.)

[0031]

Table 2 Example composition (% by weight) 1 2 3 4 5 6 7 Nonionic surfactant NA 25 15 32 NB 25 154 NC 25 N-D 25 Clay mineral MA 7 7 5 5 7 MB 3 4 iminocarboxylic acid (salt) IA 5 5 5 10 8 IB 7 Oil absorbing carrier TA 3 3 6 TB 5 5 5 5 Production method B B A A B B B A-type zeolite (slurry) 16 16 26 26 10 16 3 (grinding aids) 10 10 10 10 10 (coated) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ash 20 20 20 20 20 20 20 sulfite Soda 1 1 1 1 2 1.5 1 SFNa 3 LAS-K 2 soap 5 fluorescent agent 0.2 0.2 0.2 0.2 0.5 0.4 0.2 enzyme 1 1 1 1 2 1.5 exuded 1 perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.2 other minor ingredients Bla Bla Bla Bla Bla Bla Bla evaluation ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solidification (%) 0 0 0 0 0 0 0 Solubility ◎ ◎ ◎ ◎ ◎ ◎ ◎ Angle of repose (゜) 35 35 35 35 35 35 38 Bulk density (g / cc) 0.9 0.9 0.9 0.9 0.83 0.85 0.9 No adhesion to granulator No No No No No detergency ratio (%) 88 88 83 83 86 87 90 Note) Bla represents the remaining amount

[0032]

Table 2 (Continued) Example composition (% by weight) 8 9 10 11 12 13 14 Nonionic surfactant NA 25 25 25 25 25 25 NB 38 Clay mineral MA 5 0.5 2 15 25 7 7 iminocarboxylic acid (salt) I-A 5 5 5 5 0.8 2 I-B 5 oil-absorbing carrier T-A 8 3 3 3 3 T-B 3 3 production method B B B B B B B A-type zeolite ( Slurry) 22 20 8 20 18 (Pulverizing aid) 10 10 10 10 10 10 10 (Coating) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ash 20 20 20 20 20 20 20 20 Sulfites 1 1 1 1 1 1 1 1 Fluorescent agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme 1 1 1 1 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Other minor components Bla Bla Bla Bla Bla Bla Bla Bla Evaluation results Exudation ◎ ○ ◎ ◎ ◎ ◎ ◎ Solidification (%) 0 5 2 0 0 0 0 Solubility ◎ ◎ ◎ ○ △ ◎ ◎ Angle of repose (゜) 40 45 40 35 35 35 35 Bulk density (g / cc) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Adhesion to granulator Slight None None None No No No washing rate (%) 90 88 88 88 87 85 87 Note Bla represents the remaining amount

[0033]

Table 4 (continued) Example composition (% by weight) 15 16 17 18 19 20 Nonionic surfactant NA 25 20 25 25 25 25 Clay mineral MA 77 77 77 77 Iminocarboxylic acid ( Salt) IA 15 25 55 55 5 5 Oil absorbing carrier TA 33 0 2 0.85 TB 1313 Production method BB A AAA A zeolite (slurry) 5 28 28 15 10 (crushing aid) ) 10 10 (Coating) 2.5 2.5 2.5 2.5 2.5 2.5 Ash 20 20 20 20 20 20 20 Sulfite 1 1 1 1 1 1 Fluorescent agent 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme 1 1 1 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.2 0.2 Other Minor components Bla Bla Bla Bla Bla Bla Evaluation results Exudation ◎ ◎ △ ○ ◎ ◎ Solidification (%) 0 0 5 3 0 0 Solubility ○ △ ○ ◎ ◎ ◎ Angle of repose (゜) 35 35 40 35 35 35 Bulk Density (g / cc) 0.9 0.9 0.9 0.9 0.9 0.9 Adhesion to granulator No No No No No No washing rate (%) 89 89 88 88 88 88 Note) Bla indicates the remaining amount

[0034]

Table 5 (continued) Comparative Example Composition (% by weight) 123 Nonionic Surfactant NA 25 25 Clay Mineral MA 7 10 Iminocarboxylic Acid (Salt) IA 55 Oil Absorbing Carrier T -A 3 3 3 Production method BB B A type zeolite (slurry) 23 20 20 (grinding aid) 10 10 10 (coating) 2.5 2.5 2.5 Ash 20 20 40 Sodium sulfite 1 1 1 Fluorescent agent 0.2 0.2 0.2 Enzyme 1 1 1 Perfume 0.2 0.2 0.2 Other minor components Bla Bla Bla evaluation result Exudation property × ◎ ◎ Solidification property (%) 200 0 0 Solubility ◎ ◎ ○ Repose angle (゜) 90 35 35 Bulk density (g / cc) 0.78 0.9 0.7 Attachment to granulator No No No washing rate (%) 88 80 23 Note) Bla indicates the remaining amount. The compounds shown in the above table are as follows. A-type zeolite (for slurry): crystalline sodium aluminosilicate (Silton SMC-480 manufactured by Mizusawa Chemical Co., Ltd., solid content 51%)
(For grinding aid): Crystalline sodium aluminosilicate (Silton B manufactured by Mizusawa Chemical Co., Ltd.) (Coating): Crystalline sodium aluminosilicate (Silton B manufactured by Mizusawa Chemical Co., Ltd.) Ash: Granulated ash (Asahi Glass Co., Ltd.) Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.) SFNa: α-sodium sulfopalmitate LAS-K: potassium linear dodecylbenzenesulfonate Soap: sodium oleate Fluorescent agent: 4,4′-bis (2 -Sulfostyryl) biphenyl disodium, Tinopearl CBS-X manufactured by Ciba Specialty Chemicals Enzyme: lipase / protease / cellulase / alcalase = 1/1/1/1 mixture The perfume has the following composition.

Perfume composition parts by weight 3,7-dimethyl-1,6-octadien-3-ol 80 3,7-dimethyl-1,6-octadien-3-yl-acetate 60 3,7-dimethyl-6-octene -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-hexylsine Namic aldehyde 60 7-acetyl-1,1,3,4,4,6-80 hexamethyltetrahydronaphthalene 3- (5,5,6-trimethyl-norbarnan-20 2-yl) cyclohexane-1-ol Beltfix 30 2-ethyl-4- (2,2,3-trimethyl-3- 10 cyclopent-1-yl) -2-butan-1-ol 10% α, α-dimethyl-p-ethylhydrocinnamic aldehyde 40 2,4-dimethyl-3-cyclohexene-1- 10 carboxaldehyde cis-3- Hexenol 10 2-trans-3,7-dimethyl-2,6-30 octadien-1-ol n-decylaldehyde 5 10-undecene-1-al 5 methylnonylacetaldehyde 5 4- (4-hydroxy-4-methylpentyl) ) -3-30 Cyclohexene-1-carboxaldehyde naphthalene-2-acetyl-1,2,3,4,6,7,830-octahydro2,3,8,8-tetramethyl 5- (2-methylene- 6,6-dimethyl-cyclohexyl) 50-4-penten-3-one 2-methoxy 4-propenylphenol 20 allylcyclohexanepropionate 10 6,7-dihydro-1,1,2,3,3-pentamethyl-5 4 (5H) -indanone 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 Perfume components having a boiling point of 230 degrees Celsius (1 atm) account for 66 in all perfumes Ratio (wt%)

[0036]

According to the present invention, a relatively large amount of a nonionic surfactant is blended by blending a clay mineral with a nonionic surfactant blended with iminocarboxylic acid or a salt thereof having excellent biodegradability. Even in this case, a granular nonionic detergent composition having excellent fluidity and solidification of detergent particles can be obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroyuki Hagiwara Inside Lion Corporation, 1-3-7, Honjo, Sumida-ku, Tokyo

Claims (2)

[Claims] 1. A granular nonionic detergent composition comprising a nonionic surfactant, a clay mineral, and an iminocarboxylic acid represented by the following general formula (I) or (II) or a salt thereof. Embedded image (In the formula, R is a hydrogen atom or a hydroxyl group, and X is a hydrogen atom, an alkali metal or an ammonium group.) 2. A nonionic surfactant, a clay mineral, and an iminocarboxylic acid or a salt thereof represented by the following general formula (I) or (II) are subjected to stirring granulation or kneading and extrusion followed by crushing and granulation. A method for producing a granular nonionic detergent composition, comprising: Embedded image (In the formula, R is a hydrogen atom or a hydroxyl group, and X is a hydrogen atom, an alkali metal or an ammonium group.)