JPH10158697A - High bulk density granular nonionic detergent composition and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high bulk density granular nonionic detergent composition which can be improved in flowability under low moisture conditions and dust generation and enhance antistatic function for a chemical fiber. SOLUTION: This detergent composition comprises (a) a nonionic surfactant, (b) a clay mineral, (c) an oil absorbing carrier, (d) a polymer chelate builder having COOM (M denotes hydrogen, an alkali metal, an alkaline earth metal, or ammonium) on one or both carbon atoms adjacent to each other in the main chain, and (e) a positively charged nitrogen atom contg. a compd. selected from the group consisting of a cationic surfactant and an ampholytic surfactant, which has a positively charged nitrogen atom in the molecule and at least partially dissolves into the above nonionic surfactant (a) and is absorbed on the clay mineral (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-bulk-density granular nonionic detergent composition capable of improving the fluidity and dusting properties under low humidity and improving the antistatic function of chemical fibers.

[0002]

2. Description of the Related Art Nonionic surfactants generally have a low foaming property, their detergency is hardly affected by the hardness of water, and they are particularly excellent in mud dirt and dispersibility at low temperatures. Furthermore, nonionic surfactants are excellent surfactants such as 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 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.

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. Further, Japanese Patent Application Laid-Open No. 5-125400
In the gazette, without spray drying a nonionic surfactant, put it in a dry granulator together with an oil-absorbing carrier, perform granulation without giving excessive heat, and coat the surface of the detergent particles with amorphous silica. However, there is disclosed a method for suppressing deterioration of 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 of deterioration in fluidity and anti-caking properties still remains. Remains.

Further, in Japanese Patent Application Laid-Open No. 62-54799, the surface of the nonionic detergent particles is coated with PEG to suppress the exudation of the nonionic surfactant, but PEG has a high affinity for water. However, when the detergent particles are placed in a highly humid environment, the surface of the detergent particles is in a melted state, and as a result, the fluidity of the detergent particles is deteriorated. 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 this case, a nonionic surfactant capable of exhibiting good detergency at a relatively low concentration as compared with an anionic surfactant which has been mainstream so far works advantageously. Furthermore, not only surfactants, but also washing builders, particularly chelate builders having a function of trapping calcium or magnesium in tap water, have a relatively low concentration, which is better than that of aluminosilicate, which has been the mainstream so far. It is considered effective to use a polymer chelate builder capable of exerting chelating power.

[0005] In recent years, abnormal weather including global warming has become a problem in the world. Even in the field of detergents, even if the weather conditions such as temperature and humidity are rapidly changing, the weather may be left for a long time. More and more people have been requesting a detergent that does not impair the quality (eg, fluidity, caking, deterioration of cleaning components, etc.). The present inventor can improve the flowability, caking resistance and solubility of detergent particles in a high-temperature and high-humidity environment by using a clay mineral and an oil-absorbing carrier in combination with a nonionic surfactant first, and furthermore, the softness to cotton cloth. It has been found that the property can be imparted. However, when a polymer chelate builder is simply added to the composition to develop a more compact detergent, unexpectedly, the flow of the detergent particles in a low-humidity environment, not in a high-humidity environment, is unexpectedly increased. A new problem arises in that the properties are deteriorated and the dust (dust generation) when using detergent is intensified. This problem is not a problem when an anionic surfactant is used as a main surfactant, and is a peculiar phenomenon that occurs only when almost or all of the surfactant is a nonionic surfactant. I understood that.

[0006] By the way, some examples of blending a polymer chelate builder into a granular detergent composition have been found in the past.
For example, JP-A-54-108814 and JP-A-5-108814
JP-A-5-38868 and JP-A-56-95996 contain an anionic surfactant, a nonionic surfactant, a methyl vinyl ether / maleic anhydride copolymer or a maleic acid / acrylic acid copolymer and a cationic surfactant. Although a low bulk density detergent composition is disclosed, the flowability of the detergent particles under low humidity due to the presence of a relatively large amount of anionic surfactant or the low content of a polymer chelate builder The problems of deterioration and increase in flour during use of the detergent did not appear remarkably. Also, because clay mineral and oil-absorbing carrier are not blended,
Nonionic surfactant exudes under high temperature environment,
Poor liquidity was a problem.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a detergent composition containing both a nonionic surfactant and a polymer chelate builder. It is an object to provide a granular nonionic detergent composition.

[0008]

Means for Solving the Problems The present inventors have first intensively investigated the causes of the above-mentioned problems, and as a result, have found that a detergent composition containing a nonionic surfactant, a clay mineral and an oil-absorbing carrier contains a polymer chelate. It has been found that the deterioration of the flowability and the increase of dust generation of the detergent particles under low humidity, which occur when a builder is blended, is due to the high water absorption properties of the polymer chelate builder. Specifically, clay minerals have the property of retaining, swelling, and forming a binder (swelling / bindering) of a nonionic surfactant by chemical adsorption by hydrogen bonding between its crystal layers in the presence of auxiliary water. . Since the nonionic surfactant / clay mineral composite binder binds the nonionic surfactant and various detergent components at a high density under a high-temperature and high-humidity environment, the resulting detergent has good fluidity and no dust generation. However, when a polymer chelate builder enters this system, water in the system is selectively deprived, so that the clay mineral cannot properly retain the nonionic surfactant and cannot be swelled or bindered. Was. This phenomenon is more pronounced the lower the humidity in the environment where the detergent particles are placed. The reason is that in a high humidity environment, the polymer chelate builder removes water from the external atmosphere because a sufficient amount of water exists in the external atmosphere rather than depriving the metastable detergent particles of water. It is considered that the above-mentioned problem did not occur in the high-humidity environment, because there was no adverse effect on the swelling and bindering of the clay mineral. On the other hand, in a low humidity environment, since there is not much water in the external atmosphere, the polymer chelate builder tries to stabilize by removing water from the inside of the detergent particles. It is considered that swelling and binder formation were inhibited, and as a result, the resulting detergent deteriorated in fluidity and dust generation. These phenomena can also be demonstrated from X-ray analysis, DSC analysis, and EPMA analysis.

Based on the above findings, the present inventors conducted further intensive studies in order to solve the above-mentioned problems. As a result, the present inventors have found that a positively charged nitrogen atom can be used together with a nonionic surfactant, a clay mineral, an oil-absorbing carrier, and a polymer chelate builder. Having a compound in the molecule, and at least partially dissolving in a nonionic surfactant, even under a low humidity environment, the clay mineral swells and becomes a good binder, and the above problems can be solved. It has been found that the antistatic function for chemical fibers, which had been poorly effective when a large amount of nonionic surfactant was present, can be improved. Furthermore, it has been found that the use of a polymer chelate builder in combination with a cationic surfactant can also eliminate stickiness that occurs when the cationic surfactant is used alone, leading to the present invention. That is, the present invention provides (a) a nonionic surfactant,
(B) a clay mineral, (c) an oil-absorbing carrier, and (d) a COOM (M represents hydrogen, an alkali metal, an alkaline earth metal or ammonium) on one or both of adjacent carbon atoms in the main chain. And (e) a positively charged nitrogen atom in the molecule, which is at least partially dissolved in the nonionic surfactant (a) and adsorbed on the clay mineral (b). The present invention relates to a high bulk density granular nonionic detergent composition comprising a charged nitrogen atom-containing compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As the nonionic surfactant used in the present invention, various nonionic surfactants can be used. Preferred nonionic surfactants include, for example, the following. (1) For example, 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, for example, an average of 3 to 30 mol, preferably 7 to
20 moles of a polyoxyalkylene alkyl (or alkenyl) ether. Among them, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As the aliphatic alcohol used here, a primary alcohol or a secondary alcohol is used. Further, the alkyl group may have a branched chain. As preferred aliphatic alcohols, primary alcohols are 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 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. (9) fatty acid alkanolamides.

Among the above-mentioned nonionic surfactants, the melting point is 40 ° C. or less, preferably 5-35 ° C., and the HLB is 9-90.
16, preferably 10 to 15 polyoxyethylene alkyl (or alkenyl) ethers, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers, and fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl esters are particularly preferably used. . Further, these nonionic surfactants may be used as a mixture. The nonionic surfactant is preferably present in the high bulk density granular nonionic detergent composition in an amount of 15 to 4%.
0% by weight, more preferably 18 to 35% by weight, particularly preferably 20 to 30% by weight. When the amount is less than 15% by weight, not only the concentration of the nonionic surfactant in the obtained detergent particles is low, but also the bulk density becomes low. Therefore, if the amount of the detergent is not increased, good detergency cannot be obtained. Is unfavorable because it results in a conflict with the compactness of on the other hand,
If it exceeds 40% by weight, it is difficult to suppress seepage and it is not preferable.

The clay mineral used in the present invention particularly belongs to the smectite group, and preferably has a crystal structure of a three-layered dioctahedral structure or a three-layered trioctahedral structure. Such a clay mineral has a cleavage property and has a layered structure. This clay mineral has a smaller oil absorption than the oil-absorbing carrier described below. Further, the clay mineral has a property of chemically adsorbing a nonionic surfactant between its crystal layers by hydrogen bonding and retaining the nonionic surfactant inside the clay mineral. The clay mineral has a property of swelling as the nonionic surfactant is retained therein. The clay mineral that can be preferably used in the present invention preferably has an oil absorption of less than 80 ml / 100 g, and more preferably 30 to 70 ml / 100 g. Specific examples of such clay minerals include, for example, montmorillonite (oil absorption: 5) as a clay mineral having a dioctahedral type three-layer structure.
0ml / 100g), nontronite (oil absorption: 40m)
1/100 g), beidelite (oil absorption: 62 ml / 1)
00g), pyrophyllite (oil absorption: 70 ml / 10
0g). As a clay mineral having a trioctahedral type three-layer structure, saponite (oil absorption: 73 m
1/100 g), hectorite (oil absorption: 72 ml / 1)
00g), Stephen site (oil absorption: 30ml / 10
0 g) and talc (oil absorption: 70 ml / 100 g). These clay minerals generally include those naturally produced and those artificially hydrothermally synthesized, but are not particularly limited. Such clay minerals may be those in which a peak derived from the spread of the clay layer detected at 10 to 20 ° in X-ray analysis and a peak derived from the three-layer structure of the clay detected at 4 to 5 ° are developed. It can be used without any particular restrictions. 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 at 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 fluidity of the resulting detergent particles in a high-temperature and high-humidity environment tends 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. Oil-absorbing carrier used in the present invention,
It is used to suppress the exudation of nonions and solidification of detergent particles under high temperature and high humidity, while improving the solubility of the detergent when the detergent is used. 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 are those having an oil absorption of 80 ml / 100 g or more, preferably 15 ml or more, according to the JIS-K5101 test method.
A substance having oil absorption of 0 to 600 ml / 100 g is suitably used. As such an oil-absorbing carrier, for example,
As silicate compounds, Tokusil N (manufactured by Tokuyama Corporation, oil absorption 280 ml / 100 g), Nipsil 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 Co., Ltd.
, 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 contained in the high bulk density granular nonionic detergent composition in an amount of 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight.
It is contained in. If this amount is less than 0.1% by weight, the solidification of the resulting detergent particles under high temperature and high humidity is liable to significantly deteriorate, which is not preferable. On the other hand, when this amount exceeds 30% by weight, the amount of fine powder of the obtained detergent particles increases, and powder is easily generated.
The polymer chelate builder used in the present invention contains COOM (M) at one or both of adjacent carbon atoms in the main chain.
Are hydrogen, alkali metals (eg, potassium, sodium, etc.), alkaline earth metals (eg, calcium,
Magnesium) or ammonium. ). Specifically, -CH (COOM) -CH ₂ - or -CH (COOM) -CH
Copolymers or polymers containing a unit represented by (COOM)-in the main chain of the molecule are included.

The polymer chelate builder is generally obtained by polymerizing or copolymerizing a monomer having an ethylenically unsaturated bond and having a carboxyl group or a salt thereof on both or one of adjacent carbon atoms. Examples of the monomer having an ethylenically unsaturated bond and having a carboxyl group or a salt thereof at both adjacent carbon atoms include, for example, maleic acid, fumaric acid, aconitic acid, and citraconic acid. Further, as a monomer having an ethylenically unsaturated bond and having a carboxyl group or a salt thereof at one of adjacent carbon atoms, for example, acrylic acid, crotonic acid, isocrotonic acid, itaconic acid, methacrylic acid, α-hydroxy Acrylic acid and the like can be mentioned. Further, other comonomers may be used in combination with the above monomers. Such comonomers include, for example, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene methyl vinyl ether, ethylene, propylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate, vinyl alcohol, acrylic acid esters, and the like. Can be Of the above monomers, it is preferable to use maleic acid, acrylic acid, or methacrylic acid.

The polymer chelate builder may be used as a mixture. The copolymer used as a polymer chelate builder in the present invention has an average molecular weight of preferably 5,000 to 200,000, more preferably 6,000 to 150,000, and particularly preferably 7000.
Those having 0 to 100,000 are used. Further, the polymer used as the polymer chelate builder is preferably from 3,000 to 100,000, more preferably from 50,000 to 100,000.
00 to 50,000, particularly preferably 5,000 to 3
000 is used. The polymer chelate builder is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight in the high bulk density granular nonionic detergent composition,
Particularly preferably, the content is 3 to 10% by weight. This amount
If the content is less than 0.5% by weight, the ability to capture calcium ions or magnesium ions in tap water is insufficient.
High cleaning power cannot be expected. On the other hand, if it exceeds 20% by weight,
The resulting detergent particles are not preferred because they tend to adhere to clothing during washing.

The compound having a positively charged nitrogen atom in the molecule and at least partially soluble in a nonionic surfactant (hereinafter referred to as a compound containing a positively charged nitrogen atom for convenience) used in the present invention includes: The following can be exemplified. (1) Cationic surfactant 1) Di long chain alkyl di short chain alkyl type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] ⁺ · X ⁻ (wherein, R ₁ and R ₂ are usually carbon atoms) Represents an alkyl group having 12 to 26, preferably 14 to 18. R ₃ and R _{4 each} have usually 1 to 4 carbon atoms, preferably 1 to 2 alkyl groups or benzyl groups, and usually 2 to 4 carbon atoms. And preferably represents 2 to 3 hydroxyalkyl groups or polyoxyalkylene groups, and X represents halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1 /
_{2SO 4, OH, HSO 4,} CH 3 CO 2 or CH ₃ -C ₆ H
₄ shows the -SO _3. Specific examples of the di-long-chain alkyl di-short-chain alkyl type quaternary ammonium salt include distearyl dimethyl ammonium salt, di-hydrogenated tallow alkyl dimethyl ammonium salt,
Dihydrogenated tallow alkylbenzene methyl ammonium salt, distearyl methyl benzyl ammonium salt, distearyl methyl hydroxyethyl ammonium salt, distearyl methyl hydroxypropyl ammonium salt, distearyl dihydroxyethyl ammonium salt, dioleyl dimethyl ammonium salt, dicoconut alkyl dimethyl ammonium And the like. Specific examples of the halogen represented by X include a chlorine atom and a bromine atom.

2) Mono-long-chain alkyltri-short-chain alkyl type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] ⁺ · X ⁻ (wherein, R ¹ usually has 12 to 26 carbon atoms; Preferably 14
And represents an alkyl group of 1818. R ₂ , R ₃ and R ₄ are usually an alkyl group having 1 to 4, preferably 1 to 2 carbon atoms,
A benzyl group, usually a hydroxyalkyl group having 2 to 4, preferably 2 to 3 carbon atoms, or a polyoxyalkylene group. X represents halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1
_{/ 2SO 4, OH, HSO 4} , CH 3 CO 2 or CH ₃ -C ₆
H ₄ —SO ₃ is shown. Specific examples of the mono-long-chain alkyltri-short-chain alkyl type quaternary ammonium salt include lauryltrimethylammonium salt, stearyltrimethylammonium salt, hydrogenated tallow alkyltrimethylammonium salt, hydrogenated tallowalkylbenzenedimethylammonium salt, stearyl Examples include dimethylbenzylammonium salt, stearyldimethylhydroxyethylammonium salt, stearyldimethylhydroxypropylammonium salt, stearyltrihydroxyethylammonium salt, oleyltrimethylammonium salt, and coconut alkyltrimethylammonium salt. Specific examples of the halogen represented by X include a chlorine atom and a bromine atom.

3) Tetra-short-chain alkyl-type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] ⁺ · X ⁻ (wherein R ₁ , R ₂ , R ₃ and R ₄ are usually carbon atoms) Is 1-4, preferably 1-3 alkyl groups, benzyl groups,
Usually, it has 2 to 4, preferably 2 to 3 hydroxyalkyl groups or polyoxyalkylene groups. X is
_{Halogen, CH 3 SO 4, C 2} H 5 SO 4, 1 / 2SO 4, O
H, shows the HSO _4, CH ₃ CO ₂ or _{CH 3 -C 6 H 4 -SO 3} . Examples of the tetra-short-chain alkyl type quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, and benzyltrimethyl. Examples thereof include ammonium hydroxide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, and trimethylphenylammonium chloride.

4) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] ⁺ .X ⁻ (wherein R ₁ , R ₂ and R ₃ are usually carbon Number 12-2
6, preferably 14 to 18 alkyl groups. R ₄ represents generally from 1 to 4 carbon atoms, preferably 1-2 alkyl group, a benzyl group, usually 2 to 4 carbon atoms, preferably 2-3 hydroxyalkyl group or a polyoxyalkylene group. X represents halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1 /
_{2SO 4, OH, HSO 4,} CH 3 CO 2 or CH ₃ -C ₆ H
₄ shows the -SO _3. Specific examples of the tri-long-chain alkyl mono-short-chain alkyl type quaternary ammonium salt include trilauryl methyl ammonium chloride, tristearyl methyl ammonium chloride trioleyl methyl ammonium chloride,
Tricoconut alkyl methyl ammonium chloride and the like. (2) Amphoteric surfactant 1) Betaines represented by the following formula

[0022]

Embedded image (Wherein, R ₁ is usually an alkyl group having 12 to 18, preferably 12 to 16 carbon atoms. R ₂ and R ₃ are each CH ₃ , C ₂ H ₅ , C ₃ H ₇ , CH2COOH, etc., and n represents an integer of 1 to _3. ) Specific examples of the above betaines include amide laurate betaine and amide ethyl betaine stearate. 2) imidazoline derivatives represented by the following formula

[0023]

Embedded image (In the formula, R ₁ is usually an alkyl group having 12 to 18, preferably 12 to 16 carbon atoms.) Specific examples of the above imidazoline derivatives include 2-
Examples thereof include alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and N-coconut fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium. 3) Phosphate type As the phosphate type, lecithin (phosphatidylcholine) represented by the following formula is preferably mentioned.

[0024]

Embedded image (Wherein, R ₁ and R ₂ usually have 14 to 22 carbon atoms,
Preferably it is a 14-18 alkyl group. The compound containing a positively charged nitrogen atom used in the present invention needs to be at least partially dissolved in a nonionic surfactant. “At least partially dissolving” means that a part or all of the positively charged nitrogen atom-containing compound dissolves in the nonionic surfactant-containing particles. As for the solubility of the compound containing a positively charged nitrogen atom in a nonionic surfactant, at 50 ° C., at least 30% by weight, preferably 40% or more, and particularly preferably 60% or more of the positively charged nitrogen atom-containing compound is added to the nonionic surfactant. It is preferred to dissolve. If this solubility is less than 30% by weight,
The granular nonionic detergent composition of the present invention has poor effect of improving fluidity and dust generation in a low humidity environment. The compound containing a positively charged nitrogen atom used in the present invention is not limited to the compounds exemplified above. Further, these compounds having a positively charged nitrogen atom in the molecule and partially or wholly soluble in the nonionic surfactant may be used as a mixture.

In the present invention, the compound containing a positively charged nitrogen atom must be adsorbed on a clay mineral.
When not adsorbed, the fluidity as a detergent decreases, the whiteness decreases, and patches tend to be caused by clay minerals. As a method of adsorbing the positively charged nitrogen atom-containing compound to the clay mineral, for example, by increasing the time during which both are contacted in the production process, for example, when producing a solid detergent in the kneading step, or stirring granulation In this case, it can be carried out by blending both of these components from the initial stage. In addition, the compound containing a positively charged nitrogen atom is transformed and becomes another compound when treated at a high temperature. For example, above 80 ° C., no positively charged nitrogen atom-containing compound is present in the resulting detergent. Therefore, a method of treating at 80 ° C. or higher in the production process, for example, when a slurry containing this compound is spray-dried at 80 ° C. or higher,
It changes to another compound with the evolution of ammonia. Therefore, the resulting detergent particles have poor fluidity and antistatic properties.

The compound containing a positively charged nitrogen atom is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, particularly preferably 1 to 10% by weight in the high bulk density granular nonionic detergent composition.
-5% by weight. If the amount is less than 0.1% by weight, the effect of improving fluidity and dust generation in a low-humidity environment is poor. On the other hand, if it exceeds 10% by weight, the obtained detergent particles are likely to solidify, which is not preferable. In the granular detergent composition of the present invention, various components can be used in combination without any particular limitation as long as they are optional components usually blended in detergent raw materials. 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) Examples of the anti-redeposition agent include polyethylene glycol, sodium carboxymethylcellulose, and polyvinyl alcohol. (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 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 high bulk density granular nonionic detergent composition of the present invention can be produced by various known methods, and is not limited by the production method. As a method of high bulk density, there is a method exemplified below. Introduce essential components consisting of nonionic surfactant, clay mineral, oil-absorbing carrier, polymer chelate builder and compound containing a positively charged nitrogen atom, and optional components such as alkali builder and fluorescent agent into kneading extruders such as kneaders and extruders. Then, after mixing and applying a shearing force to form a granulated product (solid detergent), the solid detergent is mixed with a pulverizing granulator such as a cutter mill in the presence of a pulverizing aid to obtain a target particle size. After crushed into a granular detergent, this is introduced into a tumbling drum, mixed with an optional component such as an enzyme or a fragrance, and has a bulk density of 0.5 g / cm ³ or more, preferably 0.6 to 1.1 g / cm ^3. And particularly preferably 0.7.
A detergent composition of 31.0 g / cm ³ is produced. In particular, it is necessary to control the discharged granules (solid detergent) so as not to exceed 80 ° C, preferably 70 ° C. By preventing the temperature of the granulated material (solid detergent) from exceeding 80 ° C., it is possible to prevent the deterioration of the compound containing a positively charged nitrogen atom, particularly the cationic surfactant, and to greatly improve the whiteness of the detergent particles. This is particularly preferable because not only can the resulting detergent improve the antistatic effect of the resulting detergent and suppress the volatilization of the cationic surfactant, thereby improving the working environment. The lower limit temperature is usually 30 ° C. from the viewpoint of producing a solid detergent having an appropriate hardness.

Further, an essential component comprising a nonionic surfactant, a clay mineral, an oil-absorbing carrier, a polymer chelate builder and a compound containing a positively charged nitrogen atom, and optional components such as an alkali builder and a fluorescent agent are mixed with a high-speed mixer or sugar. Introduced into an internal agitation type granulator such as a mixer, a Lodige mixer, a Henschel mixer, and agitated and granulated to obtain a granular detergent having a target particle size. It is mixed with an optional component and has a bulk density of 0.5 g / cm ³ or more, preferably 0.6 to 1.1 g / cm ³ , particularly preferably 0.7.
Detergent compositions of 11.0 g / cm ³ can also be prepared. The detergent particles thus produced may be subjected to a coating treatment by adding a coating agent in a rolling drum, for example. Thereby, the flow characteristics can be further improved. As the coating agent, a fine powder having a JIS 200 mesh sieve passing amount of 50% or more is suitable. As a material, for example, carbonate such as sodium carbonate, calcium carbonate, magnesium carbonate, amorphous silica, calcium silicate, Silicate zeolites such as magnesium silicate, 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.

An enzyme, a fragrance and the like can be added to the detergent particles thus produced. The obtained high bulk density granular nonionic detergent composition of the present invention has an average particle size of 300 to 2000 μm, preferably 350 to 1500 μm.
m, particularly preferably 400 to 1000 μm, and the bulk density is 0.5 to 1.2 g / cm ³ , preferably 0.6 to 1.1 g / cm ³ ,
Particularly preferably, it is 0.7 to 1.0 g / cm ³ .

[0030]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, in Examples and Comparative Examples, each sample was evaluated by the following test methods. The storage conditions of the granular nonionic detergent composition prior to the test described below 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 ). × height 18.5
1.2 kg of the detergent was placed in a cm box, and stored in a thermo-hygrostat at 50 ° C. and 85% RH for 30 days. [Detergency test] Clean cotton cloth (cotton cloth No. 60 designated by the Japan Oil Chemical Society, 5 × 5 cm) in a dirt bath having the following artificial dirt composition:
After immersion, the water was squeezed with two rubber rolls to make the amount of adhered dirt uniform. After drying this soiled cloth at 105 ° C. for 30 minutes, the surface of the cloth was rubbed left and right 25 times. Of these, those with a reflectance of 42 ± 2% were used as dirty cloth. 60 pieces of the soiled cloth and 12 g of the sample detergent were put into a two-tub washing machine (CW-225 type, manufactured by Mitsubishi Electric Corporation), and the temperature was set at 15 ° C. and 30 ° C.
After washing with 10 liters of water (3 ° DH) for 10 minutes,
Dehydrated for 1 minute. Then, rinsing for 3 minutes with 30 liters of water at 15 ° C. 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 K / S = (1−R / 100) ² / (2R / 100) (Formula of Kubelka-Munk) Soil composition (% ) Ratio (%) 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 (Nippon Oil Chemical Association) 0.5)

[Solubility test] Tap water cooled to 5 ° C. was gently stirred with a stirrer, 5 g of detergent was added thereto, and the mixture was stirred for 8 minutes. After the undissolved particles were dried at 105 ° C. for 2 hours, the weight of the undissolved particles was weighed, and the dissolved residue was calculated by the following equation. Dissolved residue (%) = ｛weight of undissolved particles (g) / 5
(G) $ 100 [cloth adhesion] 2-tub washing machine (Mitsubishi Electric Corporation, CW-
225 type), prepare 30 liters of tap water at 5 ° C,
Put a total of 1.5 kg of two dark blue cotton shirts, two black acrylic sweaters, two black nylon slips and five skin shirts as charge cloth, make a hollow in the center of the cloth to be washed, and put 30 g of detergent there. Intensively. After leaving the detergent immersed in water for 2 minutes, it was washed with a weak stream of water for a washing time of 5 minutes. After natural drainage and dehydration for 1 minute, the amount of detergent particles (aggregates) adhering to the cloth was visually evaluated according to the following criteria. ◎: No deposit is observed. ○: Slight deposit is observed. Δ: Slight deposit is observed. ×: Many deposits are observed.

[Fluidity test] Based on JIS Z2502, the granular nonionic detergent composition was stored in an atmosphere shown in the table of Examples for 3 days, and then the fluidity of the detergent particles was measured. [Dusting test] 2-tub washing machine (Mitsubishi Electric Corporation, CW
225), a spoonful (approximately 25 g) of detergent was dropped from a height of about 70 cm into an empty washing machine, and the state of dust generation was visually evaluated according to the following criteria. ◎: No dust generation is observed. ○: Dust generation is slightly observed. Δ: Dust generation is slightly observed. X: Dust generation is observed. [Exudation test] After storage under the above conditions, all detergents are taken out and the box is removed. The degree of bleeding of the contact portion with the detergent inside was evaluated visually by the following criteria. ◎: No exudation was observed. ○: Exudation was slightly observed. Δ: Exudation was observed a little. X: Exudation was observed much. [Solidability test] After storing under the above conditions, open the upper part of this container. After carefully moving the sieve on a sieve of JIS standard 4 mesh and gently vibrating the sieve, the weight on the sieve and the total weight were measured, and the solidification 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. [Antistatic test] A 2-tank washing machine (CW manufactured by Mitsubishi Electric Corporation) was applied to 1 kg of pretreated acrylic jersey and 15 g of sample detergent.
-225 type), 15 ℃, 30 liters of water (3
(DH) for 10 minutes and then dehydrated for 1 minute.
Then, after rinsing with 30 liters of water at 15 ° C. for 3 minutes and dehydrating for 1 minute twice, the cloth to be washed was washed for 48 minutes.
Air dried indoors for hours. Next, add HONE to this cloth to be washed.
STMETER (SHISHIDO & Co. LTD.
10kV) for 30 seconds, and then measured the half-life until the charged voltage was reduced to 5 kV. The shorter the half life, the higher the antistatic effect. [Whiteness test] The b value (degree of yellowness) of the detergent particles was measured with a Hunter whiteness meter. The lower the b value, the less yellowing of the detergent particles and the higher the whiteness. [Production Method 1] After preparing a slurry by dissolving or dispersing a nonionic surfactant, a clay mineral, an oil-absorbing carrier, a compound containing a positively charged nitrogen atom, a component other than an enzyme and a fragrance, and a polymer chelate builder in water, 29 this slurry
Spray drying was performed at 0 ° C. to obtain dried particles. Next, the dried particles and a nonionic surfactant solution in which a clay mineral, an oil-absorbing carrier, and a compound containing a positively charged nitrogen atom are dissolved are put into a continuous kneader (KRC-4 type, manufactured by Kurimoto Iron Works Co., Ltd.), The mixture was kneaded to produce a solid detergent at 50 ° C. This solid detergent was put into a Fitzmill (manufactured by Hosokawa Micron Corporation, Model DKASO6) together with zeolite as a grinding aid, and
The pulverization treatment was performed in the presence of 0 ° C. cold air until the average particle diameter became 400 to 600 μm. Finally, zeolite was added in the tumbling drum to coat the obtained detergent particles, and an enzyme and a fragrance were added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 450 to 550 μm).

[Production Method 2] Components other than a nonionic surfactant, a clay mineral, an oil-absorbing carrier, an enzyme and a fragrance, a polymer chelate builder and a compound containing a positively charged nitrogen atom are dissolved or dispersed in water, and a slurry is prepared. After preparation, this slurry was spray-dried at 290 ° C. to obtain dried particles. Next, the dried particles, a nonionic surfactant, a clay mineral and an oil-absorbing carrier are continuously kneaded (KR, manufactured by Kurimoto Iron Works Co., Ltd.)
C-4) and kneaded to produce a 50 ° C. solid detergent. This solid detergent was used together with zeolite as a grinding aid together with Fitzmill (manufactured by Hosokawa Micron Corporation, DK
(ASO6 type), and pulverized in the presence of 10 ° C. cold air until the average particle size became 400 to 600 μm. Finally, the obtained detergent particles are coated in a tumbling drum, and the obtained detergent particles are coated, and an enzyme and a fragrance are added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 450 to 550).
μm).

[Production Method 3] A slurry is prepared by dissolving or dispersing components other than a nonionic surfactant, an oil-absorbing carrier, an enzyme and a fragrance, a polymer chelate builder, a compound containing a positively charged nitrogen atom, and a clay mineral in water. After that, the slurry was spray-dried at 290 ° C. to obtain dried particles. Subsequently, the dried particles, a nonionic surfactant and an oil-absorbing carrier are continuously kneaded (KRC-4 type, manufactured by Kurimoto Tekko Co., Ltd.).
, And kneaded to produce a solid detergent at 50 ° C. This solid detergent is mixed with zeolite as a grinding aid and Fitzmill (manufactured by Hosokawa Micron Corp., Model DKASO6).
And the average particle size is 400 to
The pulverization process was performed until the thickness became 600 μm. Finally, zeolite was added in the tumbling drum to coat the obtained detergent particles, and an enzyme and a fragrance were added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 450 to 550 μm).

[Production method 4] A slurry is prepared by dissolving or dispersing a component other than a nonionic surfactant, a clay mineral, an oil-absorbing carrier, a compound containing a positively charged nitrogen atom, an enzyme and a fragrance, and a polymer chelate builder in water. After that, the slurry was spray-dried at 290 ° C. to obtain dried particles. Then
The dried particles and a nonionic surfactant solution in which a clay mineral, an oil-absorbing carrier, and a compound containing a positively charged nitrogen atom are dissolved are charged into a Lodige mixer (M-20, manufactured by Matsubo Co., Ltd.). Stir and granulate at 400C to obtain an average particle diameter of 400-6
Granulation was performed until the thickness became 00 μm. Finally, zeolite was added in the tumbling drum to coat the obtained detergent particles, and an enzyme and a fragrance were added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 450 to 550 μm).

[Production Method 5] A slurry is prepared by dissolving or dispersing a component other than a nonionic surfactant, an oil-absorbing carrier, a compound containing a positively charged nitrogen atom, an enzyme and a fragrance, and a polymer chelate builder in water. , This slurry to 29
Spray drying was performed at 0 ° C. to obtain dried particles. Next, the dried particles, a nonionic surfactant, a compound containing a positively charged nitrogen atom and an oil-absorbing carrier are continuously kneaded (manufactured by Kurimoto Tekko Co., Ltd.
KRC-4) and kneaded to produce a solid detergent at 50 ° C. Fitzmill (manufactured by Hosokawa Micron Co., Ltd.)
DKASO6) and pulverized in the presence of 10 ° C. cold air until the average particle diameter becomes 400 to 600 μm. Finally, the detergent particles obtained by adding zeolite in a tumbling drum were coated, and a clay mineral, an enzyme, and a fragrance were added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 4).
50-550 μm).

[Production Method 6] Components other than a nonionic surfactant, a clay mineral, an oil-absorbing carrier, a compound containing a positively charged nitrogen atom, an enzyme and a fragrance, and a polymer chelate builder are dissolved or dispersed in water, and a slurry is prepared. After preparation, this slurry was spray-dried at 290 ° C. to obtain dried particles. Next, the dried particles and a nonionic surfactant solution in which a clay mineral, an oil-absorbing carrier, and a compound containing a positively charged nitrogen atom are dissolved are put into a continuous kneader (KRC-4 type, manufactured by Kurimoto Iron Works Co., Ltd.), The mixture was kneaded to produce a solid detergent at 85 ° C. Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKASO6 type) using this solid detergent together with zeolite as a grinding aid.
And the average particle size is 400 to
The pulverization process was performed until the thickness became 600 μm. Finally, zeolite was added in the tumbling drum to coat the obtained detergent particles, and an enzyme and a fragrance were added to obtain a high bulk density granular nonionic detergent composition (average particle diameter: 450 to 550 μm).

[Raw Materials] The nonionic surfactant (A), clay mineral (B), oil-absorbing carrier (C), polymer chelate builder (D) and positively charged nitrogen-containing material used in Examples and Comparative Examples were used. Compound (E) is as follows.

Nonionic surfactant (1) A-1 C _12-13 H _25-27 O (CH ₂ CH ₂ O) ₇ H (Conol 20P manufactured by Shin Nippon Rika Co., Ltd. (primary alcohol, carbon number 1)
2, branching degree 0%) and Diadoll 13 manufactured by Mitsubishi Chemical Corporation
(Primary alcohol, 13 carbon atoms, degree of branching 50%) and an alcohol mixed at a weight ratio of 1: 4, polyoxyethylene alkyl ether obtained by adding 7 mol of ethylene oxide on average, manufactured by Lion Chemical Co., Ltd., trade name : NALG-8
3) (2) A-2 C 13 H 27 O (CH 2 CH 2 O) 7 (CH 3 CHCH 2) 3 H
(Polyoxyethylene polyoxypropylene alkyl ether obtained by adding an average of 7 mol of ethylene oxide and an average of 3 mol of propylene oxide to Diadol 13 (primary alcohol, carbon number 13, branching degree 50%) manufactured by Mitsubishi Chemical Corporation) (3) A-3 polyoxyethylene sorbitan monooleate (polyoxyethylene sorbitan fatty acid ester obtained by adding an average of 20 mol of ethylene oxide to sorbitan monooleate, TO-10, manufactured by Nikko Chemicals Co., Ltd.)

Clay mineral (1) B-1 Ca montmorillonite (BPW00, manufactured by Meiwa Sangyo Co., Ltd.)
9, Oil absorption 50ml / 100g) (2) B-2 activated bentonite (EX available from SUD CHEMIE)
-M703, oil absorption 53 ml / 100 g) (3) B-3 Na montmorillonite (manufactured by Toyshun Yoko Co., Ltd., Wenger 2)
3, yellow, oil absorption 55 ml / 100 g) Oil absorbing carrier (1) C-1 amorphous sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., oil absorption 170 ml / 100 g) (2) C-2 amorphous water-containing amorphous Silicic acid (Tokuseal N manufactured by Tokuyama Corporation, oil absorption 280 ml / 100 g)

Polymer chelate builder (1) D-1 Maleic acid / acrylic acid (= 7/3) copolymer sodium salt (manufactured by BASF, Sokalan (registered trademark) CP)
5, average molecular weight 50,000) (2) D-2 sodium polyacrylate (manufactured by Nippon Pure Chemical Co., Ltd., Julimer AC-10S, average molecular weight 5,000) positively charged nitrogen-containing compound (1) E-1 di Hardened tallow dimethylammonium chloride (manufactured by Lion Akzo Co., Ltd., Arcard 2HT flake, solubility in nonionic surfactants A-1 to 60%) (2) E-2 benzyltrimethylammonium chloride (manufactured by Lion Akzo Co., Ltd.) (3) E-3 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (Lion Chemical Co., Ltd.)
Manufactured by Enazicol C-40H, Nonionic Surfactant A-
(4) E-4 (reference) Cationic cellulose (manufactured by Lion Corporation, Leogard GP, solubility in nonionic surfactants A-1 to A-3) 10
%)

[0043]

[Table 1] Table 1 Example 1 2 3 4 5 Kind of production method 1 1 1 1 1 Essential component A-1 25 25 25 25 25 A-3 11 1 11 B-1 77 77 77 C-2 44 44 4 D-155 55-55 E- 13--0.2 0.8 E-2--3---- E- 3--3 -- Optional component zeolite 25 25 25 25 25 25 Sulfite 11 11 1 Soda ash 20 20 20 23 22 Fluorescent agent A 0.2 0.2 0.2 0.2 0.2 Enzyme A 11 11 11 Fragrance 0.2 0.2 0.2 0.2 0.2 2 Other small components Bla * Bla Bla Bla Bla Bla Evaluation results Fluidity 25 ° C 20 RH% 35 45 35 40 40 25 ° C 50 RH% 35 40 35 45 40 25 ° C 70 RH% 35 35 35 35 35 35 25 ° C 85 RH% 35 35 35 35 35 35 45 ℃ 85RH% 3 35 35 35 35 dusting ◎ ○ ◎ ○ ◎ antistatic property (sec) 15 30 20 25 20 Bulk density (g / ml) 0.9 0.9 0.9 0.9 0.9 exudation resistance ◎ ◎ ◎ ◎ ◎ Solidification (%) 000 00 Detergency (%) 85 85 85 85 85 Dissolution residue (%) 000 00 Whiteness 2 2 2 2.5 2.3 Cloth adhesion ◎ ◎ ◎ ◎ ◎ Mu NO NO nothingness stickiness-free Note) Bla, it means the remainder.

[0044]

[Table 2] Table 1 (continued) Example 6 7 8 9 10 Kind of manufacturing method 1 1 1 1 1 Essential component A-1 25 25 25 25 25 A-3 1 1 1 1 1 B-1 7 7 7 7 7 C-2 4 4 4 4 4 D-1 55 0.8 2 12 E- 179 3 33 3 Optional component zeolite 25 25 29 28 18 Sulfite 11 11 11 Soda ash 16 14 20 20 20 Fluorescent agent A 0.20. 2 0.2 0.2 0.2 Enzyme A 1 1 1 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.2 Other small amount components Bla Bla Bla Bla Bla Bla Evaluation result Fluidity 25 ° C 20 RH% 35 35 35 35 35 25 ℃ 50RH% 35 35 35 35 35 25 ℃ 70RH% 35 35 35 35 35 25 ℃ 85RH% 35 35 35 35 35 45 ℃ 85RH% 35 35 35 35 35 dusting ◎ ◎ ◎ ◎ ◎ band Antistatic ability (seconds) 15 15 15 15 15 Bulk density (g / ml) 0.9 0.9 0.9 0.9 0.9 Exudation property ◎ ◎ ◎ ◎ ◎ Solidification property (%) 1 300 0 Detergency (%) 85 85 80 83 88 Residue of dissolution (%) 0 0 0 0 Whiteness 2 2 2 2 2 Adhesion to cloth ◎ ◎ ◎ ◎ ○ Stickiness None None None None None

[0045]

[Table 3] Table 1 (continued) Example 11 12 13 14 15 Kind of manufacturing method 1 11 1 1 1 Essential component A-1 257-2012 A- 2-718 18 1025 A-3 12 21 21 B- 17 15 15- 0.5 B-2-10 102 -C-1 -0.268 C-24 -0.8610 D-1 186 6--D-2---66 E-13 2.5-2.5 -E- 3--2.5-2.5 Optional component zeolite 12 10 16 10 10 Sulfurous acid 15 4 3 2 Soda ash 2014 14 10 17 10 Fluorescent agent A 0.20 0.4 0.1 0.2-Fluorescent agent B-0.1 0.3 0.1 0.1 SKS-10 15552 Enzyme A121-Enzyme B-1222 Fragrance 0.20 .1 0.1 0.3 0.5 other minor ingredients Bla Bla Bla Bla Bla evaluation results fluidity 2 ℃ 20RH% 35 35 35 37 40 25 ℃ 50RH% 35 35 35 37 40 25 ℃ 70RH% 35 35 35 37 40 25 ℃ 85RH% 35 35 35 37 40 45 ℃ 85RH% 35 35 35 40 45 dusting ◎ ◎ ◎ ◎ ○ Antistatic ability (sec) 15 17 17 17 17 Bulk density (g / ml) 0.9 0.8 0.85 0.9 0.9 Exudation ◎ ◎ ◎ ◎ ○ Solidification (%) 05 3 0 0 Detergency (%) 88 80 83 88 88 Dissolution residue (%) 0 5 3 0 0 Whiteness 2 2.5 2.3 1.5 0.5 Adhesion to cloth △ ○ ○ 0 ◎ Stickiness None Nothing no nothing

[0046]

[Table 4] Table 1 (continued) Comparative Example 1 2 3 4 5 Kind of production method 1 1 1 1 1 Essential component A-1 25 25 25 25 25 25 A-3 11 1 11 B-1 77 7-77 C-2 44 44- 4 D-15 55 55 -E-1 -33 33 E-4 (reference)-3 ---Type of production method 11 1 1 1 Optional component zeolite 25 25 25 25 30 sulfite 11 11 11 Soda ash 23 20 27 24 20 Fluorescent agent A 0.2 0.2 0.2 0.2 0.2 Enzyme A 11 11 11 Fragrance 0.2 0.2 0.2 0.2 0.2 2 Other minor components Bla Bla Bla Bla Bla Bla Evaluation results Fluidity 25 ° C 20 RH% 90 80 60 60 40 35 25 ° C 50RH% 70 65 60 40 35 25 ° C 70RH% 45 45 60 40 35 25 ° C 85 RH% 40 40 60 40 35 45 45 ℃ 85R % 40 40 90 40 35 dusting × × ◎ ◎ ◎ antistatic property (sec) 300 240 20 25 15 Bulk density (g / ml) 0.9 0.9 0.8 0.9 0.9 exudation property ◎ ◎ ○ × ◎ Solidification (%) 000 30 30 Detergency (%) 85 85 85 85 75 Dissolution residue (%) 000 300 Whiteness 6 5.8 87 6 Cloth adhesion ◎ ◎ ◎ × ◎ Sticky None None Slightly large

[0047]

[Table 5] Table 1 (continued) Example 16 17 18 19 20 Kind of production method 1 1 1 1 1 Essential component A-1 25 25 25 25 25 A-3 11 1 11 B-3 7 77 7 7 C-2 44 44 4 D-1 5.5 5 5 5 E-1 3 0.2 0.87 9 Optional component zeolite 25 25 25 25 25 25 Sulfite 11 11 11 Soda ash 20 23 22 16 14 Fluorescent agent A 0.2 0.2 0.2 0.2 0.2 Enzyme A 1 1 1 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.2 Other small components Bla * Bla Bla Bla Bla Evaluation result Fluidity 25 ° C 20RH% 35 45 40 35 35 25 ℃ 50RH% 35 45 40 35 35 25 ℃ 70RH% 35 35 35 35 35 25 ℃ 85RH% 35 35 35 35 35 45 ℃ 85RH% 35 35 35 35 35 dusting ◎ ○ ◎ ◎ ◎ Antistatic ability (Sec) 15 25 20 15 15 Bulk density (g / ml) 0.9 0.9 0.9 0.9 0.9 Exudation property ◎ ◎ ◎ ◎ ◎ Solidification property (%) 0 0 0 13 Detergency (%) 85 85 85 85 85 Dissolution residue (%) 0 0 0 0 Whiteness 2 3 2.5 2 2 Adhesion to cloth ◎ ◎ ◎ ◎ ◎ Stickiness None None None None None

[0048]

[Table 6] Table 1 (continued) Comparative Example Example Comparative Example 6 7 21 8 9 Kind of Production Method 2 3 4 5 6 Essential Component A-1 25 25 25 25 25 25 A-3 11 1 1 1 B-3 7 7 7 7 7 C- 2 4 4 4 4 4 D-1 5 5 5 5 5 E-1 3 3 3 3 3 Optional component zeolite 25 25 25 25 25 25 Sulfurous acid 11 11 11 Soda ash 20 20 20 20 20 Fluorescent agent A 0. 2 0.2 0.2 0.2 0.2 Enzyme A 11 1 11 1 Fragrance 0.2 0.2 0.2 0.2 0.2 Other minor components Bla * Bla Bla Bla Bla Bla Evaluation result Fluidity 25 ℃ 20RH% 90 90 35 60 80 25 ℃ 50RH% 70 70 35 60 65 25 ℃ 70RH% 45 45 35 60 45 25 ℃ 85RH% 40 40 35 60 40 45 ℃ 85RH% 40 40 35 90 40 dusting × × ◎ ○ antistatic performance (in seconds) 300 300 20 20 220 Bulk density (g / ml) 0.9 0.9 0.9 0.8 0.9 exudation resistance ◎ ◎ ◎ ○ ◎ solidifying (%) 0 0 0 0 0 detergency (%) 85 85 85 85 85 residue dissolved (%) 0 0 0 0 0 whiteness 12 12 3 8 8 (mottled) cloth adhesion ◎ ◎ ◎ ◎ ◎ stickiness Mu NO NO Some No arbitrary The components are as follows: Zeolite: crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd.) SKS: crystalline layered sodium silicate (manufactured by Hoechst Japan, SKS-6) Sulfite: sodium sulfite (manufactured by Shinshu Chemical Co., Ltd., anhydrous sodium sulfite) Soda Ash: Heavy sodium carbonate (Granular ash, manufactured by Asahi Glass Co., Ltd.) Fluorescent agent A: 2: 4,4'-bis (2-sulfostyryl)
Biphenyl disodium (Cino Geigy, Tinopearl CBS-X) Fluorescent agent B: 1: 4,4'-bis (4-amino-6-morpholino-1,3,5-triazinylamino) stilbene disulfonic acid (Sumitomo Chemical Whitex S
A) Enzyme A: 7/2 (weight ratio) mixture of alkaline protease granules and alkaline lipase granules (a mixture of Savinase 12T / Lipolase EX = 7/2, manufactured by Novo Nordisk) Enzyme B: Alkaline protease granules (Novonor (Durazyme 8T, manufactured by Disc Co.) The fragrance 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%)

[0050]

According to the present invention, COOM is added to one or both of (a) a nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, and (d) an adjacent carbon atom in the main chain. (M
Represents hydrogen, an alkali metal, an alkaline earth metal or ammonium. And (e) a compound containing a positively charged nitrogen atom in the molecule and at least partially dissolving in the nonionic surfactant, thereby reducing the humidity. The fluidity and dusting properties under have been improved, the antistatic function of the chemical fiber can be improved, and the whiteness has been further improved,
A high bulk density granular nonionic detergent composition is obtained. For example,
When one of the components of the present invention is missing, the fluidity, dust generation, antistatic properties, and the like are inferior to those of the detergents of the examples. When the compound containing a positively charged nitrogen atom is spray-dried at a temperature of 80 ° C. or higher (Comparative Examples 6, 7 and 9), or when this compound is post-added to detergent particles as in Production Example 5 (Comparative Example) In 8), since the compound containing a positively charged nitrogen atom disappears or is not adsorbed on the clay mineral, the fluidity, antistatic ability, and whiteness are inferior.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3:14 3:37 3:08 3:26 3:33) (72) Inventor Seiji Abe 1-chome, Sumida-ku, Tokyo 3-7 Inside Lion Corporation

Claims (4)

[Claims] 1. A nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, and (d) one or both of adjacent carbon atoms in the main chain contain C.
A polymer chelate builder having an OOM (M represents hydrogen, an alkali metal, an alkaline earth metal or ammonium); and (e) a nonionic surfactant (a) having a positively charged nitrogen atom in the molecule, A high bulk density granular nonionic detergent composition comprising a positively charged nitrogen atom-containing compound adsorbed on the clay mineral (b) at least partially dissolved in the clay mineral (b). 2. The high bulk density granular nonionic detergent composition according to claim 1, wherein the compound containing a positively charged nitrogen atom is a compound selected from the group consisting of a cationic surfactant and an amphoteric surfactant. 3. A nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, and (d) a carbon atom in one or both of adjacent carbon atoms in the main chain.
A polymer chelate builder having an OOM (M represents hydrogen, an alkali metal, an alkaline earth metal or ammonium); and (e) a nonionic surfactant (a) having a positively charged nitrogen atom in the molecule, And at least partially dissolve in the clay mineral (b), and knead the compound containing a positively charged nitrogen atom at a temperature of 80 ° C. or less to form a solid detergent, and then crush the solid detergent. A method for producing a bulk density granular nonionic detergent composition, comprising: 4. A nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, and (d) one or both of adjacent carbon atoms in the main chain contain C.
A polymer chelate builder having an OOM (M represents hydrogen, an alkali metal, an alkaline earth metal or ammonium); and (e) a nonionic surfactant (a) having a positively charged nitrogen atom in the molecule, A nonionic detergent composition having bulk density, characterized in that a positively charged nitrogen atom-containing compound adsorbed on the clay mineral (b) is at least partially dissolved in the clay mineral (b) and stirred and granulated at a temperature of 80 ° C. or lower. Production method.