JPS58117295A - Fragrant granular detergent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic granular detergent containing a fragrance, bentonite, and an enzyme. The invention relates to a stable aromatic granular detergent that does not cause

Normally, when cloth foil is washed, the fiber tissue shrinks? Wake up and be flexible? and the texture deteriorates. Therefore, in order to improve this point, conventionally, when flushing the water, it is first washed with detergent, then thoroughly rinsed with clean water, and in the final stage, a cationic surfactant or other A method of adding softeners has been used.

However, as can be seen from the table, this method requires a large amount of water for rinsing and requires repeated dehydration, which places a great burden on the user in terms of time and labor.

Therefore, what could be done to alleviate this burden, such as non-soap synthetic detergent compounds, organic or inorganic detergent builders, and certain smectite clays with specific cation exchange properties? Combined detergent composition
512), non-soap synthetic detergent compounds, organic or inorganic builders, specific cation exchange properties? A detergent composition (Japanese Unexamined Patent Application Publication No. 1982-3) has been proposed, which is a combination of a specific smectite clay with a cationic antistatic agent and the like.

By the way, are fragrances usually used to give detergents an aromatic effect? Blending is being done.

However, if fragrances are mixed into detergents together with the above-mentioned smectite clay as has been done in the past, the fragrance effect may not appear or the fragrance may change in quality, making it impossible to obtain the desired fragrance effect. cause problems.

On the other hand, it is known to improve groove cleaning ability by adding enzymes to laundry detergents (for example, Japanese Patent Publication No. 37-1120, Japanese Patent Publication No. 38-26465, Japanese Patent Publication No. 43-21).
Publication No. 04, etc.). However, when fragrances are added to detergents that contain enzymes, the enzymes are altered by the fragrances, resulting in a strange odor, which also reduces their effectiveness. This is accompanied by the problem that the desired fragrance effect cannot be obtained due to the fragrance being degraded by enzymes.

In order to solve these problems, special auxiliary agents are added to prevent deterioration of each ingredient and decrease in efficacy, but the range of application is limited and special chemicals are required. Therefore, it has the disadvantage of being disadvantageous in terms of cost, and cannot be said to be fully satisfactory in practical terms.

The present inventors have overcome these drawbacks and created stable enzymes, bentonite and fragrances without adding any auxiliary agents. (After extensive research, we found that by combining a certain fragrance Y proteolytic enzyme and bentonite with specific properties, and blending it with a non-soap synthetic surfactant, We found a way to achieve the objective, and based on this knowledge, we completed the present invention.

That is, the present invention provides 8α-12-oxide-13,1
4,15,16-titranobutane, iso-bornyl acetate, 2-methyl-5-isopropylphenol,
Geraniol, leaf acetal, methylheta naphthyl ketone, 3-phenylpropatol, β-phenylethyl alcohol, Santarex, caron, tertiary-sade, 6゜7-hydro-1.1,2.3-pentyl-4 (3H) -indanone, 4-acetyl-6-
tert-butyl-1,1-dimethylindane, dihydromircenol, 2,5-dimethylhebutanol-2,
2,6゜6-) At least one fragrance selected from IJ methyl-1-crotonyl-2-cyclohexene, innisinol, γ-methylionone, and terpineol, bentonite with a hydroxyl value of 25 or more, and protein decomposition The present invention provides an aromatic granular detergent comprising an enzyme and at least one non-soap synthetic surfactant selected from neutral surfactants such as anionic surfactants and nonionic surfactants.

In the present invention, it is necessary to use the above-mentioned specific fragrances, and these fragrances have the following chemical structures.

8α-12-oxide-13,14,15,16-tetranolapdan-bornyl acetate 2-methyl-5 isopropylphenol OH Geraniol leaf acetal methyl-β-naphthyl ketone 3-phenylpropatol β-phenylethyl alcohol Santa LEXSTAR CHARISDE H These fragrances may be used alone or in combination of two or more.

In the present invention, in addition to the above fragrances, optional ingredients for mixed fragrances such as acetoketer, anethole, anisylaldehyde, isobutyquinoline, cinnamic alcohol, cis-dismone, coumarin, doupicar, acetalbite ethyl Phenylethyl acetal, galasolide, silane, heptabale, hydrodopic aldehyde, linalool, mensonate, tilcinnamate, methylphenylacetate, -vinyl acetate, tetrahydromgol, liptur, and the like can be used.

The blending amount of the fragrance in the present invention is selected in consideration of the use of the detergent, usage conditions, etc., but usually based on the total
It is selected within the range of 0.01-0.5 weight, preferably 0.1-0.3 weight. This is 0. If the weight ratio is less than 01, the flavoring effect will be insufficient, while if the weight ratio is 0.5 weight, undesirable results such as deterioration and deterioration of fragrance and enzymes will result.

The bentonite used in the present invention needs to have a hydroxyl value of 25 or more, preferably 30 to 60.

The name "bentonite" was originally given to a highly swellable clay whose main component is montmorillonite (hereinafter referred to as Na-type montmorillonite), whose exchangeable cation is sodium, but it is now broadly defined as montmorillonite. It is used in all clays that contain clay minerals such as montmorillonite, saponite, hectorite, sauconite, and nontronite, which belong to the group clay minerals (this group is sometimes called smectite).

The bentonite used in the present invention exhibits the characteristic of having a hydroxyl value of 25 or more among bentonites in the latter broad sense. This hydroxyl value is based on a dry standard, excluding adhering water and adsorbed water between the eyebrows, and can be measured, for example, according to the method of HAJ Engineering 5K-0070.

In the case of bentonite whose exchangeable cation is mainly calcium (monomolylon) Y as a main component, the above method shows that the hydroxyl value is less than 25, although it has a great softening effect on fabrics. It is sometimes measured as The reason why such a phenomenon occurs has not yet been elucidated, but in such cases, when all exchangeable cations are converted to sodium by treatment with sodium carbonate, etc., and then measured. True hydroxyl value can be obtained. In addition, almost all of the cations in other ingredients in detergents are sodium, and during washing,
In this case, the exchangeable cation of bentonite is probably sodium (sodium), and in that sense, the hydroxyl group of bentonite, which is the main component of Oa-type montmorillonite, is replaced with exchangeable cation sodium. It is reasonable to measure it.

The Montmorillonite group clay mineral is a layered clay with a three-layered crystal structure as the basic unit, and exchangeable cations such as sodium 1, potassium, Clay that has ions and protons such as magnesium and galcium? When dispersed in water, exchange reactions occur with other cations present in the water. In this exchange reaction, the number of exchangeable cation equivalents per unit weight, that is, the cation exchange capacity ill (Cation Exchange Cap
The higher the acity (hereinafter abbreviated as 0, E, C), the higher the ability to capture cations such as calcium ions in water. 71)'L, between the ion exchange ability of this clay and the hydroxyl value used in the invention,
There is no direct relationship (C!, E, O, of bentonite are merely indirect factors for the purity of the montmorillonite group clay minerals contained therein.

The pentonite used in the present invention preferably has a particle size of 5 to 800 μm, particularly 50 μm.
m (Tyler standard sieve 270 mesh opening) ~5
00 μm (32 mesh opening) is suitable. This bentonite may exist separately from particles consisting of other detergent components such as surfactant components and virgoo components, or it may be uniformly present as extremely fine particles in particles consisting of these detergent components ρ. It may be dispersed and present.

In the present invention, bentonite is usually blended in an amount of 1 to 30% by weight based on the entire composition, but especially in a range of 5 to 15% by weight.
It is preferable to mix within the weight range. If this blending amount is less than 1 weight width, the fabric will have an insufficient softening effect,
Moreover, even if the weight range exceeds 30 weight, no further softening effect will be obtained, and natural clay containing iron will unnecessarily adhere to the fabric as an impurity. This is undesirable because it may cause yellowing, and the flavoring effect of the blended fragrance may deteriorate.

The enzyme used in the present invention is a proteolytic enzyme that exhibits activity in a temperature range of 5 to 85°C, preferably 15 to 65°C, and a pH of 3.5 to 13, preferably 7 to 10.5, such as "Alcalase". "〔Product name,
The enzyme commercially available as Novo Indus (IJ-GmbH, Denmark) can be mentioned. The amount to be added is appropriately selected depending on the conditions of use of the detergent, but is usually in the range of 1 to 40, preferably 5 to 20, per 9 kg of the total composition. If the compounding cap is less than 1 Anson unit, the cleaning power of the detergent cannot be improved, and even if it is more than 40 Anson units, no particular difference in cleaning effect is observed and unpleasant odors are likely to occur.

The non-soap synthetic surfactant used in the present invention is selected from anionic surfactants and nonionic surfactants. Those used in cleaning agents, such as alkali metal salts or magnesium salts of alkylbenzenesulfonic acids having alkyl groups having 10 to 16 carbon atoms, sodium alkyl sulfates having 11 to 18 carbon atoms, and α-olefins having 10 to 20 carbon atoms. Alkali metal salt or magnesium salt of sulfonic acid, carbon number 8-2
Examples include alkali metal salts or magnesium salts of sulfuric acid esters of ethylene oxide adducts of higher alcohols, and sodium alkanesulfonates having 10 to 22 carbon atoms.

In addition, as a non-soap synthetic nonionic surfactant,
Those used in ordinary cloth cleaning agents, such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc., with HLB in the range of 8 to 8. is suitable.

These non-soap synthetic surfactants may be used alone or in combination of two or more, and the blending amount usually ranges from 2 to 40 weights, preferably 2 to 40 weights, based on the total amount of the composition. 10-30 weight ratio.

Note that the amount of nonionic surfactant in the composition of the present invention is limited because it tends to prevent clay, which is mainly composed of minerals belonging to the montmorillonite group, from dispersing into extremely thin particles in water. Preferably, it does not exceed about 15 weight ti.

The composition of the present invention may also contain other components commonly used in general detergent compositions, if necessary. These include, for example, fabric recontamination inhibitors such as polyethylene glycol (PEG) and carboxymethyl cellulose (CMC), cleaning aids such as sodium sulfate, stimulants, dyes, and bleaching agents. Water can also be added.

The composition of the invention is usually used in granular form.

Generally, granular detergents are prepared by kneading surfactant components, builders, additives, etc. with water to form a highly concentrated slurry, and granulating this slurry.

In the present invention, if bentonite is directly blended into the slurry in this manner, it exists as fine particles uniformly dispersed in the detergent particles. Since bentonite also acts as a thickener, the amount of bentonite that can be added to a highly concentrated slurry made by kneading detergent ingredients with water is usually about 5% by weight based on the amount of water in the slurry. Therefore, if more bentonite is to be incorporated into a detergent, it must be added as separate particles as described above.

In this way, the uninvented aromatic granular detergent is prepared by forming a highly concentrated slurry of the non-seven-skinned synthetic surfactant, bentonite, and the various additives mentioned above, which are added as desired, and adding the fragrance and enzymes mentioned above to this slurry. It is prepared by adding and granulating.

The aromatic granular detergent of the present invention stably contains fragrances, enzymes, and bentonite without deterioration over a long period of time, emits a fragrance, and has excellent cleaning power, so it is suitable as a laundry detergent for household and commercial use. It is.

Next, the present invention will be explained in more detail with reference to Examples.

Incidentally, the fragrance stability and enzyme activity of the granular detergents in Examples were tested as follows.

200 g of a granular detergent composition containing aroma stable fragrance o and isi was collected,
Place a light shield in a carton (15X11X3-5 crn) and use it as a test sample.

To check the stability against temperature, this sample was heated at 30°C and 8°C.
04 In order to check the stability against RH atmosphere and high temperature, it was placed in a constant temperature room at 40°C, and the stability of the fragrance was evaluated after 20 days.

This judgment was made by three experienced olfactory sensory judges based on the following criteria, and is shown as an average evaluation.

○------ No change in aroma △------ Slight change in aroma The amount was removed, 1N caustic soda was added to swell it, 160 mJt of 0.05M boric acid aqueous solution was added, the pH was adjusted to 10.5 with 1N caustic soda, and then 200 m/! Prepare cicazein water bath solution by diluting with water until

Separately, prepare a sample solution by dissolving about 10% of granular detergent in pure water to make a total volume of 11%, and dispense this into 4 test tubes each containing 1.0% (7%).

Next, two of these bottles were treated with casein water-soluble fi5.
00d was first heated to 37°C, mixed with ρ), and then stored in a water tank at 37°C. After 30 minutes, add 5.00 g of 0.44 M IJ chloroacetic acid solution to each test tube, stir (d), return to the water tank, and drain after 30 minutes.

On the other hand, in the remaining two test tubes, 55% of the trichloroacetic acid solution was added.
．． After adding 00- and stirring ρ), add casein aqueous solution 5
．． 00- is added, stored in a water tank, and after 30 minutes, filtered in the same manner as above to obtain a blank.

The difference between the optical density values of the sample and blank at a wavelength of 275 mμ is measured using a colorimeter for these tear fluids, and the enzyme amount is determined using the prepared calibration curve and evaluated according to the following criteria.

5...Residual enzyme approximately 0.51 4...ll O,4&3...u 0.3g 2...ll 0.2. ! i'1...
tt0. Below IJ, the calibration curve is for enzyme 0
．． Accurately weigh 5 g, dilute the solution to 1 liter with pure water, and add granular detergent 2.0. ? It was prepared by adding the enzyme into about 50% of pure water containing 100% of the enzyme, adjusting it to a predetermined enzyme concentration, and analyzing the 100% of the enzyme.

Example 1 Granular detergents having the compositions shown below were prepared using various perfumes shown in Table 1.

Ingredients Heavy 1 fragrance
0.15 Bentonite (Introductory Brain 25) 10 Alcalase (manufactured by Novo) 0.5 Sodium silicate 10 Sodium carbonate 10 Cafoxymethylcellulose
0.6 water
Table 1 shows the aroma stability and fermentation activity of the granular detergent thus obtained.

Example 2 Granular detergents were prepared in exactly the same manner as in Example 1, except that instead of the perfume in Example 1, various blended perfumes shown in Table 2 were used.

The aroma stability and enzyme activity of the granular detergent thus obtained are shown in Table 2.

Claims (1)

[Claims] 18α-12-oxide-13,14,15,16-titranolabdan, iso-bornyl acetate, 2-methyl-5-isopropylphenol, geraniol, leaf acetal, methyl beta naphthyl ketone, 3-phenyl propatool, β-phenylethyl alcohol,
Santarex, Caron, Tertiary Sade, 6,
7-Sihydro1゜1.2.3-pentyl-4(3H)
-Indanone, 4-acetyl-6-tert-butyl-
1,1-dimethylindane, dihydromircenol, 2
．． 5-Dimethylhebutanol-2,2,6,6-drimethyl]-Crotonyl-2-cyclohexene, isonicinol, γ-methylionone, and terpineol, at least one fragrance selected from D.? , hydroxyl value 25
An aromatic granular detergent comprising at least one non-soap synthetic surfactant selected from anionic surfactants and nonionic surfactants, along with the above bentonite and proteolytic enzyme. 2. The aromatic granular detergent according to claim 1, wherein the fragrance content is 0.01 to 5 parts by weight based on the total amount of the composition. 6 The content of bentonite is 1 to 3 based on the total amount of the composition.
The aromatic granular detergent according to claim 1, which has a weight coefficient of 0. 4. The aromatic granular detergent according to claim 1, wherein the enzyme content is in the range of 1 to 40 Anson units per IKg of the total composition.