JPH01193397A - High-density granular concentrated detergent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition, having aroma of powder almost equal to that of a low-density detergent, aroma of washing liquid and residual aroma of clothes without changing aromatic tone even after preservation for a long period, by blending a granulated material of a perfume clathrate powder with a powdery detergent. CONSTITUTION:A liquid perfume component, stable in an alkali or zeolite system and having low volatility is sprayed on a high-density granular concentrated detergent material or added as a master powder prepared by premixing with part of detergent components and powdering the resultant mixture to a detergent. On the other hand, a liquid component, unstable in an alkali or zeolite system and having high volatility is included in a compound having the ability of inclusion and then granulated to provide a granulated material of a perfume clathrate, which is subsequently added to a powdery detergent and afford the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high-density granular concentrated detergent, and more particularly:
Dense granular concentrated detergent compositions that provide a consumer-desirable fragrance.

[Conventional technology]

In recent years, demand for high-density concentrated powder detergents has been increasing from the viewpoint of resource conservation, transportation of detergents, and convenience for housewives in terms of carrying and storing detergents.

High-density powder detergents include JP-A-48-61511, JP-A-53-36508, and JP-A-58-13.
No. 2093, etc., all of them are related to the general composition, manufacturing method, or solubility improvement of high-density powder detergents, but none are related to the problem of fragrance of high-density powder detergents.

[Problem to be solved by the invention]

Adding a specific amount of fragrance to detergent is generally done to mask the ingredients of the detergent, impart an appropriate fragrance to the powder, washing liquid, and washed clothes, and increase the product value. This is necessary.

However, high-density granular concentrated detergents (here, high-density refers to detergents with bulk specific gravity of 9.5 g/cm or more) are different from conventional low-density detergents (usually with bulk specific gravity of about 0.3 g/cm'). ), the content of active ingredients such as surfactants is increased, the density is increased, and the amount (weight and volume) used per wash is reduced (e.g. 40g/301 to 25g).
/301) Therefore, if fragrance is added in the same proportion as conventional low-density detergent, the amount of fragrance ingredients in the washing liquid and laundry will decrease according to the amount used, and the fragrance of the washing liquid and the washed clothes will decrease. There was a drawback that the residual fragrance was too weak.

In order to compensate for this drawback, it would be easy to think of increasing the fragrance added to the detergent, but this would cause the problem that the scent of the detergent powder itself would become too strong, causing discomfort. Fragrances contain hydroxyl groups, aldehyde groups, ester groups, ketone groups, nitro groups, amino groups, ether groups,
It has functional groups such as cyano groups or double bonds,
In general, alkaline and zeolite-based detergents such as heavy powder laundry detergents tend to be easily decomposed, denatured, or polymerized. Therefore, increasing the perfume-imparting rate is undesirable because it increases the likelihood of decomposition and denaturation of the perfume.

Regarding the stabilization of fragrances, West German Patent No. 3020269 discloses that the storage stability of fragrances is improved by incorporating fragrances into anionic detergents as inclusion powders with cyclodextrin, and that the anionic surfactants in detergents improve the storage stability of fragrances. It is stated that the fragrance is released immediately and quantitatively at the moment of use of the laundry detergent. However, this technique does not teach the problem of fragrance in dense powder detergents.

[Means to solve the problem]

The inventors of the present invention have carried out intensive studies on the addition of fragrance to high-density granular detergents, and as a result, have found that the problem can be solved by using granules of fragrance inclusion powder, and have completed the present invention.

That is, the present invention provides a high-density granular concentrated detergent composition, which is characterized in that it contains a granulated product of fragrance inclusion powder obtained by clathrating a fragrance into a compound having clathration ability.

As the clathrate compound used in the present invention, β-cyclodextrin is best, but β-cyclodextrin derivatives such as methylated β-cyclodextrin, α-cyclodextrin, T-cyclodextrin, etc. can also be used.

The method of clathrating the fragrance with an clathrate compound and turning it into powder can be the method used in -Moinai. Usually, while stirring a slurry of clathrate compounds or an aqueous solution system,
It can be obtained by gradually adding a fragrance, filtering off the fragrance inclusion complex, and drying it. The fragrance and the clathrate compound are used in a molar ratio of 0.8 to 1.2.

Granulation of the powdered fragrance is carried out in a dry or wet manner using a binder. Here, the dry method or wet method refers to whether water is used as a binder or not, and an organic compound having a melting point or softening point of 40° C. to 160° C. is used as the binder. Examples of organic compounds having a melting point or softening point of 40° C. to 160° C. include polyethylene glycol with a molecular ff of 11,500 to 20,000, polyethylene glycol alkyl ether having an alkyl group with a carbon number of Cs to C2, and a carbon number of 08 to C2. Polyethylene glycol alkylphenol ether with alkyl group, carbon number 01□~
Examples include fatty acids having a C37 alkyl group, block polymers of ethylene oxide and propylene oxide, and the like.

The powdered fragrance is granulated by an extrusion granulation method, a transfer granulation method, etc. with the addition of a binder and, if necessary, a filler such as Glauber's salt, a powder property improver such as silica, and other additives.

During granulation, the following amounts are used: 20 to 80 parts by weight (hereinafter abbreviated as "parts") of the fragrance inclusion powder, 5 to 35 parts of the binder, 15 to 50 parts of the filler, and 0 to 5 parts of the powder property improver. It is better.

The average particle diameter of the granules is 100 to 1500μ, preferably 200 to 1300μ, more preferably 300 to 1000μ.
It is preferable to granulate it in μ. It is desirable that the amount of particles less than 100μ and more than 1500μ is 5% by weight (hereinafter abbreviated as %) or less. Granules are usually 0.1-5% in high-density granular detergents.
It is blended.

The perfume used in the present invention is not particularly limited.

However, the method for imparting fragrance to high-density granular detergents is preferably as follows.

That is, a liquid fragrance material that is alkaline or zeolite-based, stable, and has low volatility is sprayed onto a high-density granular concentrated detergent fabric, or it is mixed in advance with a part of the detergent ingredients and added as a powdered master powder. , alkaline, or zeolite-based, unstable or highly volatile liquid fragrance materials are clathrated in a compound with inclusion ability and then granulated to form a fragrance inclusion powder granule, which is then added to a granular detergent. It is.

Conventionally, commonly used alkali or zeolite-based fragrance materials that are stable and have low volatility include alcohols, esters of secondary or tertiary alcohols, ketones,
Examples include ether and the following fragrances.

(i) Alcohol synthetic sandals, benzyl alcohol, phenylethyl alcohol, styralyl alcohol, dimethylbenzyl carbinol, etc. (ii) Ketontenchrome, acetophenone, benzophenone, α-
Damascone, methyl amyl ketone, etc. (iii) Ester hedeion, hexyl acetate, isoamyl acetate, etc.
(iv) Ether diphenyl oxide, amyl phenyl ethyl ether, cedranba, neroline yara yara, anethole, etc. (v) Other aldehydes C-14 peach, coumarin, pentalide, etc.
These fragrance materials such as musk ambrette and methyl anisranilate are conventionally added to granular detergent fabrics by spraying or as a master powder mixed with some of the detergent ingredients.

Examples of unstable or highly volatile alkali- or zeolite-based fragrances that have conventionally been considered unsuitable for alkali or zeolite-based fragrances include the following.

(1) Monoterpene hydrocarbons and their derivatives (i) Monoterpene hydrocarbons limonene, α-pinene, β-pinene, terterpirun,
Myrcene, etc. (11) Derivatives (alcohols) Citronellol, linalool, geraniol, etc. (ketones)! -Menthone, 2-carvone, camphor, etc. (esters) Cinnamyl acetate, geranyl acetate, tervinyl acetate, etc. (aldehydes) Citral, citronellol, (Others) Citronellyl nitrile, geranyl nitrile, eucalybutol, etc. (2) (1) Excluding <ch ~ Aldehyde of CI5 08
~C14 aldehyde, lyral, anisaldehyde,
Benzaldehyde, α-n-amyl cinnamic aldehyde, α-n-hexyl cinnamic aldehyde, Lilial, heliothrobin, cinnamic aldehyde, etc. (3) Excluding (1) <Formic acid or acetate ester benzyl formate of CS to CI5, Phenylethylformate, anisyl acetate, benzyl acetate, phenylethyl acetate-1-, cinnamyl acetate, p-
One or more of the above fragrances such as tert-butyl cyclohexyl acetate, isoamyl acetate, cis-3-hexyl acetate, etc. are included in a compound having inclusion ability and then granulated to obtain a fragrance inclusion granule. It is blended into high-density granular detergent systems.

Although the composition of the high-density granular concentrated detergent composition in the present invention is not particularly limited, the following components are generally blended as necessary.

(1) Alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkanesulfonate, saturated or unsaturated fatty acid salt, α-sulfo fatty acid salt or ester, alkyl or alkenyl ether Anionic surfactants such as carboxylic acid salts (the content of anionic surfactants is usually 25-50%, preferably 30-40%)
% 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) Surfactants such as betaine type amphoteric surfactants, sulfonic acid type amphoteric surfactants, phosphate ester type surfactants, and cationic surfactants (4) Alkali such as silicates, carbonates, and sesquicarbonates Agent (5) Zeolite (aluminosilicate), orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, isocitrate, polyacrylic acid, polyacetal carboxylic acid, etc. Divalent metal ion scavenger (6) polyvinyl alcohol, polyvinylpyrrolidone,
Anti-recontamination agents such as carboxymethyl cellulose and polyethylene glycol (7) Bleaching agents such as sodium percarbonate, sodium percarbonate, and sodium hydrogen peroxide adducts (8) Enzymes such as protease, esterase, lipase, and cellulase (9) Others Manufacture of high-density concentrated granular detergents with ingredients commonly used in detergents such as anti-caking agents, bleach activators, peroxide stabilizers, antioxidants, fluorescent dyes, blue tinting agents, light-activated bleaches, fragrances, etc. There are no particular limitations on the method, but for example, an alkali agent and an acid-resistant detergent component are added to an unneutralized anionic surfactant, and after neutralization, zeolite and tripoly are added and pulverized, or spraying. It can be manufactured by a method of increasing the bulk density by granulating a powdered detergent by drying.

Bulk density is 0.58/Cm3 or more, preferably 0.5-1
．． 2g/cm3, more preferably 0.7-1.2g/c
It is desirable that it is m3.

The particle size of the high-density concentrated granular detergent is preferably 2,000μ or less, and 3% or less is 125μ or less, more preferably 125μ or less.
It is desirable that μ or less be 1% or less.

〔Effect of the invention〕

The present invention makes it possible to obtain a high-density granular detergent that exhibits almost the same strength of powder scent, washing liquid scent, and residual fragrance on clothing as conventional low-density detergents. Another advantage is that the aroma does not change even after long-term storage. Furthermore, it is now possible to use fragrances that were previously thought to be alkali or zeolite-based and unstable or highly volatile, increasing the degree of freedom in creating fragrances and creating fragrances that were not previously possible. Now I can give.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited by the following examples.

Example 1 and Comparative Examples 1 to 5 Low-density detergents and high-density granular concentrated detergents with the formulations shown in Table 1 were manufactured, and the scent of the detergent powder and the scent of the washing liquid were scented with the fragrance compositions shown in Table 2. Table 3 shows the results of a comparative study of the scent, the residual fragrance of washed clothes, and the stability of the fragrance.

Table 1: Detergent composition (All numbers in the table are weight%) Each component in Table 1 shows the following.

LAS, linear alkylbenzene sulfonic acid soda (C
+z~C13) AO3; α-olefin sulfonic acid soda (016~C
+s) Soap; Beef tallow soap (C+a~Cps) Nonion; Polyoxyethylene alkyl ether (C,
□ ~ C13 + - Punishment - = 10) Polyethyl glycol; Average molecular weight: about 13.000 Small amounts of additives: Fluorescent dye, enzymes, etc. In contrast to Composition 1 in Table 1, Composition 2 contains each component other than sodium sulfate at 1.6% each. With twice the amount, 1/1 of composition 1
With a usage weight of 1.6, the concentration of each component will be the same as the composition 1,
This is a so-called concentrated composition.

Table 2 shows the fragrance composition used next.

Table-2 Fragrance composition Lemon Muguet style *Phenylethyl alcohol 20% (1)
Limonene 20% (1) Citral 5% (2) Lilial 10% (2) α
-Hexyl cinnamic aldehyde 20% (2) Lyral 15% (3) Benzyl acetate 10% total
Ioo% Below, we will explain the manufacturing method of low-density detergents and high-density granular concentrated detergents, perfume adding methods, fragrance evaluation methods, and fragrance stability, but the manufacturing method is a preferred example and is particularly limited to this. It is not something that will be done.

■) Detergent manufacturing method From Composition 1 in Table 1, prepare a slurry with 50% by weight of hydrated bone by removing 2% by weight of zeolite and a small amount of additives such as enzymes, etc., which are preferably dry-mixed later. Composition 1 with a bulk density of 0.30 g/cm' was prepared by dry mixing the components initially removed with the powder obtained by spray drying
A low density detergent was obtained.

On the other hand, from Composition 2 in Table 1, a slurry containing 50% by weight of hydrated bone was prepared by removing components such as 10% by weight of zeolite and a small amount of additives such as enzymes, which are preferable to be dry mixed afterwards.
The powder obtained by spray-drying it is put into a high-speed mixer (stirring transfer granulator, manufactured by Fukae Kogyo Co., Ltd.),
Add 5% by weight of zeolite moistened with 1% by weight of water, crush and granulate it, then add 3% by weight of zeolite, crush and granulate, and add a small amount of remaining 2% by weight of zeolite to the resulting particles. By dry mixing the additives, the bulk density is 0.75g.
/cm' of composition 2 was obtained.

2) Incense adding method To 100 parts of the above powdered detergent, (A) The above blended fragrance was sprayed.

(B) The perfume ingredients marked with * in the above prepared perfume were sprayed, and the other perfume ingredients were made into perfume inclusion powder by the following method and mixed together.

(C) The perfume ingredients marked with * in the above prepared perfume were sprayed, and the other perfume ingredients were made into perfume inclusion body powder granules by the following method, and these were mixed.

The cleaning agent obtained by the above method was evaluated.

<Preparation of fragrance inclusion body powder and its granules> Celldex N (manufactured by Japan Food Processing Co., Ltd.) was poured into 200 d of warm water at 60°C.
18.0 g of β-cyclodextrin) was added,
- Completely dissolves the cyclodextrin. 2.5 g of mixed fragrance was added to this and stirred for 3 hours. After addition of the prepared fragrance, a water-insoluble precipitate was formed and an inclusion phenomenon was observed. After filtration, 20 g of fragrance inclusion complex powder was obtained by freeze-drying.

After mixing the powder of the clathrate with the following composition, a granulated product was obtained using an extrusion granulator manufactured by Fuji Powder Co., Ltd. (model EXMS-1). This was classified using a 16.32 mesh sieve to obtain a granulated product.

Particle size distribution of granules; average particle size: 670 μm, 500 μm or more, 1.0%, less than 100 μm, 4.0% 3) Evaluation of fragrance (i) Evaluation of fragrance of detergent powder Pour detergent into a wide-mouthed glass bottle with a capacity of about 50 cm.
Immediately after the lid was opened, 10 trained panelists evaluated the strength of the scent using a paired comparison method with a standard detergent. As a reference detergent, 100 parts by weight of the low-density detergent of Composition 1 was scented with 0.12 parts by weight of fragrance according to scenting method A.

The evaluation criteria are shown below.

Evaluation points Evaluation criteria 2 Much stronger than the standard detergent 1 Slightly stronger than the standard detergent 0 Same as the standard detergent - 1 Slightly weaker than the standard detergent - 2 Much weaker than the standard detergent The evaluation results are based on the number of people who gave each rating and the number of people who gave each rating. It is expressed as the sum of products with the evaluation score.

In other words, the larger the value, the stronger the scent.

(ii) Rating of scent of laundry liquid: 20"C tap water 301%, composition 1 low density detergent 40"C tap water 301%
Immediately after dissolving 25 g of the high-density granular concentrated detergent of Ml Sei 2 in a washing machine, the strength of the fragrance of the washing liquid was evaluated in the same manner as in (i).

(Mountain) Add 1 kg of cotton underwear to the washing liquid used in (ii) for evaluation of fragrance retention on washed clothes, wash for 10 minutes, and then
Dehydrate for 1 minute, then add 20°C tap water to 151/mi
After rinsing at a flow rate of n for 6 minutes, dehydrating for 3 minutes, and air-drying it indoors overnight,
Evaluation was made in the same way as in (i) by pairwise comparison with those treated with the same standard detergent.

4) Evaluation of fragrance stability: 50cmf of detergent in a wide mouth glass bottle with a capacity of 100ct113
Put the lid on and heat at -5°C, 130°C, 140°C for 20 minutes.
The fragrance was stored for several days, and the stability of the fragrance was determined by sensory evaluation by a panel of 10 people.

○ No change 0 to Δ Slight change △ Clear change Table 3 Umbrella fragrance application rate indicates the weight part of fragrance added to 100 parts by weight of detergent.

Applicant's agent Kaoru Furutani

Claims (1)

[Scope of Claims] 1. A high-density granular concentrated detergent composition, characterized in that it contains a granulated product of fragrance inclusion powder obtained by including a fragrance in a compound having inclusion ability. 2. When flavoring a high-density granular concentrated detergent with a fragrance consisting of an alkali- or zeolite-based liquid fragrance component that is stable and has low volatility and an alkali- or zeolite-based liquid fragrance component that is unstable or highly volatile, Alternatively, a zeolite-based liquid fragrance ingredient that is stable and has low volatility may be sprayed onto a high-density granular concentrated detergent fabric, or it may be pre-mixed with a portion of the detergent ingredients and added as a powdered master powder to create an alkaline or zeolite-based fragrance ingredient. A high-density product characterized by including an unstable or highly volatile liquid fragrance component in a compound having inclusion ability, and then granulating it to form a fragrance inclusion granule, which is then added to a granular detergent. Method for adding fragrance to granular concentrated detergent.