JP2617507B2 - High density granular concentrated detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to high-density granular concentrated detergents, and more particularly, to high-density granular concentrated detergent compositions that provide a scent desirable for consumers.

[Conventional technology]

In recent years, demands for high-density powder concentrated detergents have been increasing from the viewpoint of resource saving, convenience in transporting detergents, and carrying and storing places by housewives.

As a high-density powder detergent, JP-A-48-61511,
JP-A-53-36508, JP-A-58-132093, etc., all relate to the improvement of the general composition, production method or solubility of a high-density powder detergent, and There was nothing related to the detergent scent problem.

[Problems to be solved by the invention]

It is common practice to add a specific amount of fragrance to detergents, to mask the raw odor of detergents, to give appropriate aroma to powder, washing liquid and washed clothes, and to enhance the commercial value. Is necessary.

However, high-density granular concentrated detergents (here, high density refers to those with a bulk specific gravity of 0.5 g / cm ³ or more) are replaced with conventional low-density detergents (those with a bulk specific gravity of usually about 0.3 g / cm ³ ). In comparison, the content of the active ingredient such as a surfactant is increased, and the density (density and capacity) per washing is reduced by increasing the density (for example, from 40 g / 30 to 25 g / 30). Therefore, when perfumed at the same ratio as the conventional low-density detergent, the amount of the fragrance component in the washing liquid and the laundry decreases according to the amount used, and the aroma of the washing liquid and the residual scent on the washed clothes are weak. There was a disadvantage that it became too much.

In order to compensate for this drawback, it is easy to consider increasing the fragrance rate to the detergent. However, in such a case, there is a problem that the scent of the detergent powder itself becomes too strong and unpleasant.

Further, the fragrance has a functional group such as a hydroxyl group, an aldehyde group, an ester group, a ketone group, a nitro group, an amino group, an ether group, a cyano group or a double bond as a fragrance group. Alkalis such as cleaning agents for
Many zeolites are susceptible to decomposition, modification or polymerization. Therefore, it is not desirable to increase the perfume rate because the perfume is likely to be decomposed and denatured.

Regarding the stabilization of the fragrance, in West German Patent No. 3020269, the storage stability of the fragrance is improved by blending the fragrance with cyclodextrin as an inclusion powder in an anionic detergent, and the anionic surfactant in the detergent is used. It is described that the fragrance is released quantitatively immediately at the moment of using the laundry detergent. However, this technique does not teach the problem of flavoring in high density powder detergents.

[Means for solving the problem]

Means for Solving the Problems As a result of intensive studies on perfuming in a high-density granular detergent, the present inventors have found that the problem can be solved by using a granulated perfume clathrate powder and completed the present invention.

That is, the present invention provides a high density of bulk density 0.7 to 1.2 g / cm ^3, characterized in that blended granules of perfume inclusion compound powder obtained by inclusion of the perfume compound having inclusion ability A particulate concentrated cleaning composition is provided.

As the inclusion compound used in the present invention, β-cyclodextrin is the best, but β-cyclodextrin derivatives such as methylated β-cyclodextrin, α-cyclodextrin, γ-cyclodextrin and the like can also be used.

A commonly used method can be used as a method for encapsulating and powdering the fragrance with an inclusion compound. Normally, while stirring the clathrate compound slurry or aqueous solution system, the fragrance is gradually added, and then the fragrance clathrate is filtered off.
It can be obtained by drying. The fragrance and the clathrate are used in a molar ratio of 0.8 to 1.2.

Granulation of the powdered fragrance is performed by a dry method or a wet method using a binder. Here, the dry type or the wet type means whether or not water is used as a binder.
Alternatively, an organic compound having a softening point of 40C to 160C is used. Examples of the organic compound having a melting point or a softening point of 40 ° C. to 160 ° C. include polyethylene glycol having a molecular weight of 1500 to 20,000, polyethylene glycol alkyl ether having an alkyl group having ₈ to ₂₂ carbon atoms, and C ₈ to C ₈ carbon atoms. Examples thereof include polyethylene glycol alkylphenol ethers having ₂₂ alkyl groups, fatty acids having alkyl groups having ₁₂ to ₃₇ carbon atoms, and block copolymers of ethylene oxide and propylene oxide.

The powdered fragrance is granulated by an extrusion granulation method, a tumbling granulation method, or the like, to which a binder and, if necessary, an extender such as sodium sulfate and a powder property improving agent such as silica and other additives are added. At the time of granulation, it is used in the range of 20 to 80 parts by weight (hereinafter abbreviated as "parts"), 5 to 35 parts of a binder, 15 to 50 parts of a bulking agent, and 0 to 5 parts of a powder property improving agent. Is good.

The granulated material has an average particle diameter of 100 to 1500 μ, preferably 200 to
It is good to granulate to 1300μ, more preferably 300 to 1000μ. Particles having a particle size of less than 100 µm and exceeding 1500 µm are desirably 5% by weight (hereinafter abbreviated as%) or less. The granules are usually incorporated in the high-density granular detergent at 0.1 to 5%.

The fragrance used in the present invention is not particularly limited.
However, the method of flavoring the high-density granular detergent is preferably as follows.

That is, a liquid perfume material which is stable in alkali or zeolite and has low volatility is sprayed on a high-density granular concentrated detergent cloth or mixed in advance with a part of detergent components and added as a powdered master powder. , Alkali or zeolite-based liquid perfume material which is unstable or highly volatile is included in a compound having an inclusion ability, and then granulated to form a perfume clathrate powder granule and then added to a granular detergent It is.

Conventionally, generally used alkali or zeolite-based stable and low volatility fragrance materials include alcohol, secondary or tertiary alcohol esters, ketones, ethers and the like. Is exemplified.

(I) alcohol synthetic sandals, benzyl alcohol, phenylethyl alcohol, styryl alcohol, dimethylbenzyl carbinol, etc. (ii) ketone tentalome, acetophenone, benzophenone, α
-Damascone, methyl amyl ketone, etc. (iii) Ester hedeion, hexyl salicylate, isoamyl salicylate, fluteate, methyl benzoate, etc. (iv) Ether diphenyl oxide, amyl phenyl ethyl ether, cedramba, nerolin yalayara, anethole, etc. (v) Other aldehide C- 14 peach, coumarin, pentalide,
These fragrance materials such as musk ambrette and methylanisulanilate are conventionally added to a granular detergent cloth as a master powder which is sprayed or mixed and powdered with a part of detergent components.

The following are examples of fragrances that are unstable or highly volatile in alkali or zeolite systems, which have heretofore been unsuitable in alkali or zeolite systems.

(1) Monoterpene hydrocarbons and derivatives thereof (i) Monoterpene hydrocarbons Limonene, α-pinene, β-pinene, terterpinolene, myrcene, etc. (ii) Derivatives (alcohols) Citronellol, linalool, geraniol, etc. (ketone) l- Mentone, l-carvone, camphor, etc. (ester) citronellyl acetate, geranyl acetate, terpinyl acetate, etc. (aldehyde) citral, citraneral, (others) citronellyl nitrile, geranyl nitrile, eucalyptol, etc. (2) (1) aldehyde C ₆ -C ₁₅ aldehyde C ₈ -C ₁₈ except, lyral, anisaldehyde, benzaldehyde, alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde,
Lilial, heliotropin, cinnamic aldehyde, etc. _{(3) (1) C 5} ~C 15 of formic acid or acetic acid ester benzyl formate except, phenylethyl formate,
Anisyl acetate, benzyl acetate, phenylethyl acetate, cinnamyl acetate, p-tert-butylcyclohexyl acetate, isoamyl acetate, cis-3-hexyl acetate, etc. One or more of the above fragrances is a compound having an inclusion ability After the inclusion, the mixture is granulated and blended into a high-density granular detergent system as a perfume clathrate granule.

The composition of the high-density granular concentrated detergent composition of the present invention is not particularly limited, but generally the following components are blended as required.

(1) Alkyl benzene 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 alkenyl ether (The content of the anionic surfactant is usually in the range of 25 to 50%, preferably 30 to 40%.) (2) Polyoxyalkylene alkyl or alkenyl Ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, fatty acid glycerin monoester, alkylamine oxide (3) betaine-type amphoteric surfactant, sulfonic acid-type amphoteric surfactant , Phosphate Surfactants such as ter-based surfactants and cationic surfactants (4) alkaline agents such as silicates, carbonates and sesquicarbonates (5) zeolites (aluminosilicates), orthophosphates, pyrophosphates, Divalent metal ion scavengers such as tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, isocitrate, polyacrylic acid, polyacetalcarboxylic acid, etc. (6) Polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyethylene Recontamination inhibitors such as glycol (7) Bleaching agents such as sodium percarbonate, sodium perborate, and sodium hydrogen peroxide adduct (8) Enzymes such as protease, esterase, lipase, and cellulase (9) Other anti-caking agents , Bleach activator, peroxide stabilizer, antioxidant Ingredients commonly used in detergents such as detergents, fluorescent dyes, bluing agents, light-activated bleaching agents, fragrances, etc. The method for producing a high-density concentrated granular detergent is not particularly limited. For example, unneutralized anionic surfactant Produced by adding an alkaline agent and an acid-resistant detergent component to the agent, neutralizing it, adding zeolite and tripoly, etc. and pulverizing it, or granulating a powder detergent by spray drying to increase the bulk density can do.

The bulk density is 0.7 to 1.2 g / cm ^2.

The particle size of the high-density concentrated granular detergent is preferably 2,000 μm or less, preferably 125 μm or less, 3% or less, more preferably 125 μm or less, 1% or less.

〔The invention's effect〕

According to the present invention, it has become possible to obtain a high-density granular detergent exhibiting the same scent of powder, scent of laundry, and residual scent of clothes, which are almost the same as conventional low-density detergents. In addition, there is an advantage that the fragrance does not change even after long-term storage. Furthermore, since the perfume which was conventionally considered to be unstable or highly volatile in an alkali or zeolite system can be used without any problem, the degree of freedom in perfume perfume is increased, and an unprecedented perfume is produced. You can now give.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 and Comparative Examples 1 to 5 A low-density detergent and a high-density granular concentrated detergent having the composition shown in Table 1 were produced, and the fragrance of the detergent powder perfumed with the fragrance composition shown in Table 2 was obtained. Table 3 shows the results of a comparative study of the scent, the residual scent of the washed clothes, and the stability of the fragrance.

Composition 2 was prepared by mixing components other than sodium sulfate by 1.6 times with respect to composition 1 in Table 1, and was 1 / 1.6 of composition 1.
It is a so-called concentrated blended composition that has the same amount of each component as the composition 1 in the weight used.

 Next, the perfume composition used is shown in Table 2.

Table 2 Flavor composition Lemon mugé * Phenylethyl alcohol 20% (1) Limonene 20% (1) Citral 5% (2) Lilyal 10% (2) α-hexylcinnamic aldehyde 20% (2) Lilyal 15% ( 3) Benzyl acetate 10% Total 100% or less, low-density detergent and high-density granular concentrated detergent manufacturing method,
The method of perfuming, the method of evaluating the fragrance, and the stability of the fragrance will be described, but the production method is a preferred example, and is not particularly limited thereto.

1) Detergent preparation From the composition 1 in Table 1, 2% by weight of zeolite and a slurry containing 50% by weight of water having a composition excluding the components such as enzymes in a small amount of additives that are desirably dry-mixed later are prepared. The low-density detergent of composition 1 having a bulk density of 0.30 g / cm ³ was obtained by dry-mixing the components first removed to the powder obtained by spray drying.

On the other hand, from the composition 2 in Table 1, 10% by weight of zeolite and a small amount of the enzyme, etc., in a small amount of additives, were dry-mixed to prepare a slurry containing 50% by weight of water with a composition excluding the desirable components and spraying it. The powder obtained by drying is put into a high-speed mixer (stirring tumbling granulator, manufactured by Fukae Kogyo Co., Ltd.), and crushed granules are added by adding 5% by weight of zeolite moistened with 1% by weight of water. Then, 3% by weight of zeolite was added, and the particles obtained by crushing and granulating were dry-mixed with the remaining 2% by weight of zeolite and a small amount of additives to obtain a composition 2 having a bulk density of 0.75 g / cm ³ . A high-density granular concentrated detergent was obtained.

2) Flavoring method (A) The prepared flavor was sprayed on 100 parts of the above powder detergent.

(B) The perfume component indicated by * in the prepared perfume was sprayed, and the other perfume components were made into perfume clathrate powders by the following method and mixed.

(C) The perfume component indicated by * in the above prepared perfume was sprayed, and the other perfume components were formed into a perfume clathrate powder granulation by the following method and mixed.

The cleaning agent obtained by the above method was evaluated.

<Preparation of perfume clathrate powder and granulated product> 18.0 of Celldex N (β-cyclodextrin) manufactured by Japan Food Processing Co., Ltd. was added to 200 ml of hot water at 60 ° C,
Completely dissolve the β-cyclodextrin. 2.5 g of the compounded flavor was added thereto and stirred for 3 hours. After adding the compounded flavor,
A water-insoluble precipitate was formed and an inclusion phenomenon was observed. After filtration, lyophilization yielded 20 g of a powder of the perfume clathrate. After the clathrate powder was mixed with the following composition, a granulated product was obtained with an extrusion granulator of Fuji Paudal Co., Ltd. (model EXKS-1). This was classified with a sieve of 16, 32 mesh to obtain a granulated product.

The particle size distribution of the granulated product; an average particle diameter of 670μ 1500μ least 1.0% 100 microns less than 4.0% 3) Evaluation of fragrance (i) about 50 cm ³ Put lid detergent wide mouth glass bottle Rated capacity 100 cm ³ of scented detergent powder, The intensity of the fragrance immediately after opening the lid was evaluated by a paired comparison method with a reference detergent by ten trained panelists.
As a reference detergent, a low-density detergent of composition 1 obtained by perfuming 0.12 part by weight of a fragrance by perfume method A was used.

 The evaluation criteria are shown below.

Evaluation points Evaluation criteria 2 Stronger than standard detergent 1 Slightly stronger than standard detergent 0 Same as standard detergent -1 Slightly weaker than standard detergent -2 Slightly weaker than standard detergent Evaluation results are based on the number of people who gave each evaluation and Expressed as the sum of the products with the evaluation points. That is, the larger the value, the stronger the scent.

(Ii) Evaluation of the aroma of the washing liquid The strength of the aroma of the washing liquid immediately after dissolving 40 g of the low-density detergent of composition 1 and 25 g of the high-density granular concentrated detergent of composition 2 in tap water 30 at 20 ° C. The evaluation was made in the same manner as in (i).

(Iii) Evaluation of residual fragrance of washed clothes Put 1 kg of cotton underwear into the washing liquid used in (ii), wash for 10 minutes, dehydrate for 1 minute, and then tap water at 20 ° C for 15 / min.
Rinse for 6 minutes while flowing at the flow rate of
After air drying overnight in a room, the intensity of the residual scent of cotton underwear was evaluated in the same manner as in (i) by a pairwise comparison with those subjected to the same treatment with a reference detergent.

4) with a lid put detergent 50 cm ³ in a wide-mouthed glass bottle Rated capacity 100 cm ³ of stability of the perfume, -5 ℃, 30 ℃, and stored 20 days at 40 ° C., the functional stability of the perfume by 10 panelists It was determined by evaluation.

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 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-69897 (JP, A) JP-A-56-44905 (JP, A)

Claims (2)

(57) [Claims] 1. A high-density granular material having a bulk density of 0.7 to 1.2 g / cm ³ , wherein a granulated product of a perfume clathrate powder obtained by encapsulating a perfume with a compound having an inclusion function is included. Concentrated detergent composition. 2. A high-density granular concentrated detergent is perfumed with a perfume comprising an alkali or zeolite-based liquid flavor component which is stable and has low volatility and an alkali or zeolite system which is unstable or has high volatility. In doing so, spray the alkali or zeolite-based stable and low volatility liquid fragrance component onto a high-density granular concentrated detergent fabric, or premix with some of the detergent components, add as a powdered master powder, It is characterized in that an alkali or zeolite-based unstable or highly volatile liquid fragrance component is included in a compound having an inclusion ability, then granulated, and added to a granular detergent after forming a fragrance inclusion complex granule. Bulk density 0.7 to 1.2
Perfume method of high-density granular concentrated detergent of g / cm ³ .