JP3459850B2 - High bulk density granular detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.
More specifically, it relates to a granular detergent composition having a high bulk density capable of optimizing the scent of detergent powder and the residual aroma of clothes after washing.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
The detergent composition contains a fragrance for the purpose of masking the original odor of the detergent composition, imparting an aroma, and imparting an aroma to the clothes after washing. However, it is difficult to maintain both the fragrance of the cleaning agent itself and the residual aroma of clothes, and great efforts have been made to develop such a fragrance.

On the other hand, in recent years, high-concentration concentrated detergents have become the mainstream on a global scale from the viewpoint of resource saving and convenience of transportation of detergents and convenience for housewives to carry and place.

However, a high-density granular concentrated detergent (high density here means a bulk specific gravity of 0.5 g / cm ³ or more)
Compared with conventional low-density detergents (usually having a bulk specific gravity of about 0.3 g / cm ³ ), the content of active ingredients such as surfactants is increased to increase the density, and the amount used per wash The amount (percentage) of the perfume component to the washing liquid and the laundry when it is scented at the same ratio as the conventional low-density detergent because it has a reduced (weight and volume) (for example, from 40 g / 30 liter to 25 g / 30 liter). However, there is a drawback that the scent of the washing liquid and the residual aroma of the washed clothes become too weak depending on the amount used.

In order to make up for this drawback, it is easily conceivable to increase the rate of perfume to the detergent, but if this is the case, there is a problem in that the scent of the detergent powder itself becomes too strong and rather causes discomfort. .

Previously, we have found that the above problem can be solved by using a perfume composition in which a perfume component having a specific vapor pressure is mixed, and have disclosed it in Japanese Patent Laid-Open No. 63-101496. However, in the fragrance composition, the fragrance is specified, and the degree of freedom in combining the fragrances is lowered. Further, JP-A-1-193397 discloses a method of including a perfume in an inclusion compound such as β-cyclodextrin, but the inclusion compound is relatively expensive, and in this method, the inclusion compound is previously prepared. It requires a step of encapsulating the perfume.

[0007]

In view of the above-mentioned present situation, the present inventors have earnestly studied a method capable of keeping the characteristics of both the scent of the powder detergent itself and the residual aroma of clothes, as a result of earnest research. It has been found that this object can be achieved by coating a powder detergent composition with an amorphous silica-based compound having a specific oil absorbing ability, and has completed the present invention.

That is, the present invention provides a perfume selected from monoterpene hydrocarbons and derivatives thereof, and perfume selected from aldehydes having from 6 to 15 carbon atoms excluding the monoterpene hydrocarbons and their derivatives, Mo Noterupen hydrocarbons And a perfume component containing a combination of perfumes selected from formic acid or acetic acid ester having 5 to 15 carbon atoms excluding its derivative.
0.1 to 1% by weight , and at least an alkaline agent
Yes to a high bulk density granular detergent composition, the surface of the granular detergent composition is covered by the amorphous silica-based compound oil absorbency of more than 100 ml / 100 g as measured based on JIS K 6220 , Monoterpene hydrocarbons and their derivatives
But limonene, α-pinene, β-pinene, terterpino
Len, myrsen, citronellol, linalool, gerani
Oar, l-menthone, l-carvone, camphor, shi
Tronellyl acetate, geranyl acetate, terpini
L-acetate, citral, citranellal, citronet
Ryl nitrile, geranyl nitrile, eucalyptol
Selected from the group consisting of monoterpene hydrocarbons and
Carbon atoms excluding derivatives 6-15 aldehydes, C ₈ -C
₁₄ aldehydes, lyral, anisaldehyde, benz
Aldehyde, α-n-amylcinnamic aldehyde,
α-n-hexylcinnamic aldehyde, lilyar
Leo, heliotropin, cinnamic aldehyde
The monoterpene hydrocarbons and their derivatives
Formic acid or acetic acid ester having 5 to 15 carbon atoms excluding body is
Benzyl formate, phenylethyl formate,
Nisyl acetate, benzyl acetate, phenyl ethyl
Luacetate, cinnamyl acetate, p-tertiary
Butyl cyclohexyl acetate, isoamyl acetate
And cis-3-hexyl acetate
The amount of coating with the amorphous silica-based compound is
0.5-10% by weight based on the total amount of the lica compound and the granular detergent composition
The present invention provides a high bulk density granular detergent composition characterized by being

The amorphous silica compound used in the present invention has an oil absorption capacity of 100 ml / measured according to JIS K 6220.
It is 100 g or more, preferably 150 ml / 100 g or more. If the oil absorption capacity of the amorphous silica compound is less than 100 ml / g, this effect cannot be obtained. The amorphous silica-based compound is an inorganic substance, which means that the content of SiO ₂ is 40% or more, preferably 70% or more in terms of anhydrous content, and those commercially available are used. You may. Amorphous silica and amorphous aluminosilicate having an average particle size of up to about 200 μm are commercially available. In the present invention, an amorphous silica compound may be selected from them. Examples of such amorphous silica compounds include Tokseal AL-1 [Tokuyama Soda Co., Ltd.], Nipseal NA [Nippon Silica Co., Ltd.], Carplex # 100 [Shionogi Pharmaceutical Co., Ltd.]
], SIPERNAT D10 (Degussa), TIXOLEX 25
Examples thereof include compounds marketed under the trade name of (Kofran Chemical Co.).

The most preferred amorphous silica compound in the present invention is an amorphous aluminosilicate represented by the following formula (A) which has an ion exchange capacity in addition to its oil absorption capacity. x (M ₂ O) ・ Al ₂ O ₃・ y (SiO ₂ ) ・ w (H ₂ O) (A) {In the formula, M represents a sodium atom and / or a potassium atom, and x, y, and w are each Represents the number of moles of the component, x is 0.7-2.
0, preferably 0.7-1.2, y 1.8-6.0, preferably 1.8
6 and w are arbitrary positive numbers. } In particular, the following general formula (B) Na ₂ O ・ Al ₂ O ₃・ m (SiO ₂ ) ・ c (H ₂ O) (B) [where m is 1.8 to 3.2 and c is a number of 1 to 6] Represents ]
What is represented by is preferable.

The amorphous aluminosilicate represented by the above general formula (A) or (B) and having a high oil absorption and a high ion exchange capacity is SiO ₂ and M ₂ O (M means an alkali metal). The molar ratio of
A _{SiO 2 / M 2 O = 1.0} ~4.0, H 2 O and M ₂ O molar ratio of
The alkali metal silicate solution is a _{H 2 O / M 2 O =} 12~200, the molar ratio of M ₂ O and Al ₂ O ₃ is _{M 2 O / Al 2 O 3} = 1.0~2.0, H 2 O the molar ratio of M ₂ O is a low alkali aluminate alkali metal salt solution which is a _{H 2 O / M 2 O =} 6.0 ~500 and 15
It is added under strong stirring at a temperature of -60 ° C, preferably 30-50 ° C. Further, an aqueous solution of alkali metal silicate may be added to the aqueous solution of alkali metal aluminate. The resulting white precipitate slurry is then cooled to 70-100 ° C, preferably 90-1.
It can be advantageously obtained by heat treatment at a temperature of 00 ° C. for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. Ion exchange capacity by this method
It is possible to easily obtain an amorphous aluminosilicate having 100 CaCO ₃ mg / g or more and an oil absorption capacity of 200 ml / 100 g or more.

In the present invention, the amorphous silica compound may be added during the granulation step of the granular detergent composition or may be added to the granulated product after the granulation step, and finally the granular detergent composition. It suffices if the composition is covered with an amorphous silica compound. Then, the fragrance component is blended by coating the granular detergent composition with the amorphous silica-based compound and then spraying it on the particle surface of the granular detergent composition. Further, the granular detergent composition may be coated with an amorphous silica-based compound carrying a fragrance component.

The coating amount of the granular detergent composition with the amorphous silica compound is 0.5 to 10% by weight based on the total amount of the silica compound and the granular detergent composition, that is, [amorphous silica compound] / [non-silica compound]. Crystalline silica compound + granular detergent composition] x 10
It is preferable that 0 is 0.5 to 10% by weight. The amount of coating is
If it is less than 0.5% by weight, the fragrance tends to remain during storage.

In addition to using the amorphous silica-based compound as a coating agent for the granular detergent composition, it is more preferable that the amorphous silica-based compound is incorporated into the granular detergent composition fabric. In that case, the amorphous silica-based compound is coated. The total amount of the amount (a) used for the above and the amount (b) compounded in the detergent dough is 10 to 30% in the final composition.
It is preferable to mix them in such a manner that the weight% is obtained.

The perfume to be blended in the high bulk density granular detergent of the present invention may be a perfume material which is stable in alkali and zeolite and has low volatility.
There are esters, ketones, ethers, etc. of secondary or tertiary alcohols, and the following fragrances are specifically exemplified. (I) Alcohol synthetic sandals, benzyl alcohol, phenylethyl alcohol, styrylyl alcohol, dimethylbenzylcarbinol, etc. (ii) Ketone tentalom, acetophenone, benzophenone, α-
Damascon, methyl amyl ketone, etc. (iii) Ester hedeion, hexyl salicylate, isoamyl salicylate, fruitate, methyl benzoate, etc. (iv) Ether diphenyl oxide, amyl phenyl ethyl ether, sedlumba, Neroline Yala Yala, anethole, etc. (v) Other Aldehide C -14 Peach, coumarin, pentalide, musk ambrette, methylanisanilate, etc. In the present invention, it is a perfume having high instability or volatility in the alkali or zeolite system, which was conventionally unsuitable for the alkali or zeolite system. Terpene hydrocarbons and their derivatives
Fragrances selected from the body, monoterpene hydrocarbons and
Selected from aldehydes having 6 to 15 carbon atoms excluding derivatives of
Fragrances and monoterpene hydrocarbons and their derivatives are excluded.
Selected from formic acid or acetic acid ester having 5 to 15 carbon atoms
A combination of flavors is included, and examples of such flavors include the following. (1) Monoterpene hydrocarbons and their derivatives (i) Monoterpene hydrocarbons limonene, α-pinene, β-pinene, terterpinolene, myrcene, etc. (ii) Derivatives (alcohol) Citronellol, linalool, geraniol, etc. (ketone) l- Mentone, l-carvone, camphor, etc. (ester) Citronellyl acetate, geranyl acetate, terpinyl acetate, etc. (Aldehyde) citral, citranellal, (other) citronellyl nitrile, geranyl nitrile, eucalyptol, etc. (2) (1) aldehyde C ₆ -C ₁₅ aldehyde C ₈ -C ₁₄ except, lyral, anisaldehyde,
Benzaldehyde, α-n-amyl cinnamic aldehyde, α-n-hexyl cinnamic aldehyde, lilial, heliotropin, cinnamic aldehyde, etc. (3) Excluding (1) C _{5 to} C ₁₅ formic acid or acetate benzyl formate , Phenylethyl formate,
In the present invention, anisyl acetate, benzyl acetate, phenylethyl acetate, cinnamyl acetate, p-tertiarybutylcyclohexyl acetate, isoamyl acetate, cis-3-hexyl acetate, etc. are added in an amount of 0.1 to 1% by weight.

[0016] High bulk density granular detergent composition in the present invention
Is an alkaline agent such as silicate, carbonate, sesquicarbonate
The other components are not particularly limited, but the following components are generally added as needed.
The blending amount of each component is not limited.

(1) Alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, α-sulfo fatty acid salt or ester, alkyl Or anionic surfactant such as carboxylic acid salt of alkenyl ether (the content of anionic surfactant is usually 25 to 50%, preferably 30 to 40%
Is the range. ) (2) Polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether,
Higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid glycerin monoester, alkylamine oxide (3) betaine type amphoteric surfactant, sulfonic acid type amphoteric surfactant, phosphate ester type surfactant, cation sex surfactant surfactant, such as (5) zeolite (aluminosilicates), orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, isocitrate, poly Divalent metal ion scavengers such as acrylic acid and polyacetalcarboxylic acid (6) Recontamination inhibitors such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyethylene glycol (7) Sodium percarbonate, sodium perborate, sodium sulfate peroxidation Bleach such as hydrogen adduct (8) Enzymes such as protease, esterase, lipase, cellulase (9) Other anti-caking agents, bleach activators, peroxide stabilizers, antioxidants, fluorescent dyes, bluing agents, photoactivation Bleaching agents, ingredients commonly used in detergents such as fragrances, etc. Although the detergent composition fabric of the present invention is a powder or granular composition, its production method is not particularly limited, and conventionally known methods can be used. . In particular, spray-dried particles obtained by spray-drying an aqueous slurry of each component having a water content of 30 to 80% by weight, preferably 35 to 60% by weight, preferably granulating the spray-dried particles to increase the bulk density Is desirable. Alternatively, a method may be used in which an unneutralized product is directly neutralized and mixed with an alkali agent such as an alkali metal hydroxide, kneaded with other washing builders, and then cooled and pulverized after mixing. . To increase the bulk density, Japanese Patent Application Laid-Open No. 61-69897, Japanese Patent Application Laid-Open No. 61-69899, Japanese Patent Application Laid-Open No. 61-69900, Japanese Patent Application Laid-Open No. 2-222498, Japanese Patent Application Laid-Open No. 2-222499, JP-A-3-33199, JP-A-5-86400, JP-A-5
The method described in JP-A-209200 can be used. Further, when the crystalline aluminosilicate is blended, a small amount may be added during the granulation or immediately before the completion of the granulation, in addition to the slurry, in order to use it as a surface modifier of the granulated product. Also,
When the crystalline layered silicate is blended, it is preferable to add it at the time of granulating the spray-dried particles and increasing the bulk density without adding them to the slurry. Further, when an alkali metal carbonate and / or an alkali metal silicate is blended, it may be added either in the slurry or in the granulation. Particularly, the alkali metal silicate is added to the slurry to have excellent powder properties. It is possible to obtain spray-dried particles, which facilitates handling in manufacturing.

The average particle size of the final particles of the granular detergent composition of the present invention is 200 to 1000 μm in order to obtain preferable powder properties.
m, especially 200 to 600 μm is desirable. Also,
The bulk density of the detergent composition of the present invention is about 0.5 to 1.0 g / cm ³ , preferably about 0.6 to 0.9 g / cm ³ .

[0019]

EFFECTS OF THE INVENTION According to the present invention, a high bulk density capable of optimally maintaining both the scenting properties of detergent particles and the residual scenting of clothes after washing, such as masking the odor of detergent fabrics and adding scents. A granular detergent composition is obtained.

[0020]

The present invention will be further described in the following examples, but the present invention is not limited to these examples.

Example Of the raw materials shown in Table 1, a surfactant (see Tables 3 and 4),
Add an amount of the oil-absorbing amorphous silica compound (see Tables 3 and 4) at the time of granulation, zeolite A, sodium carbonate, sodium sulfite and DM type fluorescent dye to a batch kneader (PNV-
1, Irie Shokai Co., Ltd.) and a liquid or semi-liquid nonionic surfactant (polyoxyethylene dodecyl ether) was gradually introduced to obtain a detergent granule. Then, the amount of the amorphous silica-based compound for surface coating shown in Tables 3 and 4 was added and mixed,
The surface was coated. Further, a fragrance having the composition shown in Table 2 was sprayed and the enzyme was after-blended to obtain a final detergent product.

With respect to the obtained granular detergent composition, the scent was evaluated by the 20 panelists in the following 5 grades, and the average value was obtained. 5: Too strong scent 4 ... Slightly strong scent 3 ... Good 2 ... Slightly weak scent 1 ... Weak scent Also, the obtained granular detergent composition should be 15 to 20 g per 30 liters of washing bath. After the clothes were dissolved and washed with a bath ratio of 1/15, clothes that had been shade-dried for 8 hours (25 ° C) were used as evaluation samples, and the residual aroma of the clothes was evaluated in the same manner as the scent of the above detergent composition. did. The results are also shown in Tables 3 and 4.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

(Note) The amorphous aluminosilicates in Table 4 are produced by the following synthesis examples. Synthesis example Sodium aluminate aqueous solution (Na ₂ O: Al ₂ O ₃ = 20.3: 2
(Adjusted by adding 2000 parts by weight of ion-exchanged water to 100 parts by weight of sodium aluminate of 8.2 (weight ratio)) 800
100 parts by weight of No. 3 water glass solution (prepared by adding 100 parts by weight of commercially available water glass) to 20 parts by weight at 60 ° C
It was heated for 20 minutes, filtered and washed. The obtained wet cake was pulverized with a crusher to obtain an amorphous aluminosilicate. The composition of the obtained amorphous aluminosilicate was determined by atomic absorption and plasma fluorescence analysis, and Al ₂ O ₃ =
It was 27.2% by weight, SiO ₂ = 21.6%, and Na ₂ O = 21.6% by weight. The oil absorption capacity was 186 ml / 100 g.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-264099 (JP, A) JP-A-3-351000 (JP, A) JP-A-63-101496 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C11D 3 / 12,3 / 50

Claims (3)

(57) [Claims] 1. A monoterpene hydrocarbon and its derivative
A perfume selected from, selected from aldehydes having from 6 to 15 carbon atoms excluding the monoterpene hydrocarbons and their derivatives
And flavor, containing 0.1-1% by weight of perfume ingredients containing a combination of perfume selected from formic acid or acetic acid ester of 5 to 15 carbon atoms excluding the motor Noterupen hydrocarbons and derivatives thereof, further containing at least an alkaline agent a high bulk density granular detergent composition, the surface of granular detergent compositions, JI
The oil absorption capacity measured based on SK 6220 is coated with an amorphous silica-based compound of 100 ml / 100 g or more, and monoterpene-based hydrocarbons and their derivatives are limonene,
α-pinene, β-pinene, terterpinolene, myrce
, Citronellol, linalool, geraniol, l-
Mentone, l-carvone, camphor, citronellil
Cetate, geranyl acetate, terpinyl acetate
Tomato, citral, citranellal, citronellil nitri
Le, geranyl nitrile, eucalyptol
With 6 carbon atoms excluding monoterpene hydrocarbons and their derivatives
15 of aldehydes, aldehyde of C ₈ ~C _14, Rira
, Anisaldehyde, benzaldehyde, α-n-a
Milcinnamic aldehyde, α-n-hexylcinna
Mick aldehyde, lilial, heliotropin, syn
It is selected from namic aldehydes and has 5 carbon atoms excluding monoterpene hydrocarbons and their derivatives.
~ 15 formic acid or acetic acid ester is benzyl form
G, phenylethyl formate, anisyl acetate
, Benzyl acetate, phenylethyl acetate,
Cinnamyl acetate, p-tert-butyl cyclohexyl
Xyl acetate, isoamyl acetate, cis-3-
It is selected from hexyl acetate, and the coating amount of the amorphous silica-based compound is the silica-based compound.
A high bulk density granular detergent composition, characterized in that it is 0.5 to 10% by weight in the total amount of the compound and the granular detergent composition . 2. Amorphous silica-based compound (a) for coating
Further contain amorphous silica-based compound (b) in addition, in the final composition (a) + (b) the total amount is 10 to 30 wt% claim 1 high bulk density granular detergent composition. 3. The amorphous silica-based compound has the following formula:
Claim 1 is an amorphous aluminosilicate represented by (A)
Or the high bulk density granular detergent composition according to item 2. x (M ₂ O) ・ Al ₂ O ₃・ y (SiO ₂ ) ・ w (H ₂ O)
(A) (In the formula, M represents a sodium atom and / or a potassium atom, x, y, w represent the number of moles of each component, and x represents 0.7 to 2.
0 and y are 1.8 to 6.0, and w is an arbitrary positive number. }