JPS627795A - Detergent composition - 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 [Industrial Field of Application] The present invention provides a detergent composition that can provide high detergency performance as well as excellent hygroscopicity and flexibility to clothing in the laundry work. relating to things.

[Conventional technology]

Conventionally, detergent compositions containing anionic surfactants as a main ingredient have been widely used for washing clothes, but clothes washed with such detergent compositions have a rough texture. This tendency was especially noticeable for items that were washed repeatedly. Therefore, after washing, a fabric softener called softer is generally used to soften the fabric.
Treatments such as antistatic treatments were often applied.

In recent years, with the aim of eliminating the double effort of cleaning and finishing, cleaning compositions have been developed that perform both cleaning and finishing in one step. However, since commercially available products use cationic surfactants to impart effects such as softening and antistatic treatment, they may interact with anionic surfactants, which are the main components of cleaning compositions. This occurs, and the intended effect cannot be sufficiently achieved by simply mixing both components, and various other efforts have been made.

For example, the crystal system of the quaternary ammonium salt is important for its dispersion and adsorption to the washed fabric in the coexistence of detergents containing anionic surfactants as main ingredients. known (Japanese Unexamined Patent Publication No. 59-30898,
JP-A-59-30899).

[Problem that the invention seeks to solve]

However, even with the above-mentioned techniques, the softening effect cannot always be obtained with good reproducibility depending on the type of clothing (fiber), and it is difficult to achieve both the softening effect and the cleaning effect.

In addition, among clothing, underwear and towels in particular are required to have not only flexibility but also water absorbency, which required further study.

In particular, the softening effect of the primary quaternary ammonium salt is caused by the lubricating effect of the lipophilic sites in the base molecules adsorbed on the fiber surface. However, this lipophilic property has the disadvantage of making clothing water repellent and reducing water absorption.

[Means for solving problems]

The present inventors have conducted intensive studies to compensate for the water absorption properties of cleaning compositions containing quaternary ammonium salts having contradictory properties.
By combining grade ammonium salts and the enzyme cellulase, it is possible to impart excellent water absorbency, especially to cellulose fibers such as cotton, and surprisingly, it also has remarkable softening performance without impairing its washing function. The present invention was completed by discovering that the present invention can be improved.

That is, the present invention provides a powdery detergent material containing an anionic surfactant, a cellulase of bacterial or fungal origin,
and general formula (1) (in the formula, R1 and R2 are C2° to CZ2 alkyl or alkenyl groups, R3 and R4 are lower alkyl groups, and halogen elements), and the long-plane distance in X61 diffraction is It is characterized by blending powder particles of a quaternary ammonium salt in which the ratio (1)/(■) of the first-order diffraction peak intensity (I) to the maximum peak intensity (IF) of the side spacing is 2.0 or less. The present invention relates to a cleaning composition.

The di-long-chain quaternary ammonium salt used in the present invention has a dissociable quaternary nitrogen as a polar group, and two of the four groups bonded to this are hydrophobic groups with a long-chain alkyl structure, The molecular shape is elongated and asymmetrical. Crystals of these substances grow in the direction of their molecular chains and in the direction in which the molecular chains are arranged in parallel. In the X-ray diffraction pattern of such a crystal, diffraction lines originating from repeating units in the molecular chain direction are obtained in the long surface region, and diffraction lines originating from repeating units in the cross section of the molecular chain are obtained in the short surface region. By specifying the degree of crystal growth in the molecular chain direction and the degree of crystal growth in the cross-sectional direction of the molecular chain, quaternary ammonium salt particles having an excellent flexibility imparting effect can be obtained.

This is determined by the ratio (I)/(n) of the first-order diffraction peak intensity (1) of the long-plane spacing and the maximum peak intensity (II) of the short-plane spacing determined by X-ray diffraction of a di-long-chain alkyl quaternary ammonium salt. is required to be 2.0 or less. If this ratio exceeds 2.0, the effect of imparting water absorption and flexibility to clothing will not be sufficient.

Such a di-long chain alkyl quaternary ammonium salt is, for example, represented by the general formula (1), and can be obtained by spray cooling a melt or by pulverizing a solid that has been cooled as it is, and can also be used as a powdery detergent. used in combination with From the viewpoint of use in conjunction with detergents, it is preferable that the particle size has an average particle size of 100 to 350μ and does not substantially contain particles larger than 500μ.If the particle size is too small, the surface area of the particles increases, so anion They are susceptible to the action of activators (and if they are not too large, they will fall off quickly even if they adhere to clothing, and the particles that adhere to clothing will be noticeable).

Further, the apparent specific gravity of the powder particles of the quaternary ammonium salt should be at least 0.25, and is particularly preferably at least 0.4.

The quaternary ammonium salt powder thus prepared is mixed and blended with a granular detergent material containing an anionic surfactant as a main component by a conventional method.

It is preferable that the amount of the quaternary ammonium salt powder added to the entire cleaning composition is 0.5 to 5% by weight (hereinafter simply expressed as %). In addition, the amount of anionic surfactant is the amount in general cleaning compositions, that is, 15 to 25
% is preferable.

Cellulases, which are one of the essential components of the present invention, can be those widely distributed in animals, plants, bacteria, and fungi, and purified fractions thereof, and are not particularly limited.

The origin of cellulase is JP-A-57-108199.
Examples include those described in No.

Among these, cellulases of bacterial or fungal origin are preferred.

Furthermore, when alkaline cellulases that retain sufficient activity even in alkaline conditions, especially alkaline cellulases of bacterial origin, are used, higher finishing and cleaning effects can be obtained. Examples of alkaline cellulases include the following.

(a) Cellulase cultured and collected from a bacterium belonging to the genus Aeromonas with the microorganism deposit number No. 2306 (see Japanese Unexamined Patent Publication No. 76287/1987) (b) The microorganism deposit number is Submission No. 1138, No. 1
Bacillus No. 139, No. 1140 and No. 1141 (
Cellulase cultured and collected from bacteria belonging to the genus Bacillus (see JP-A-50-28515) (c) Snail; Dolabella auricula 5ola
Cellulase (B
iochem.

J., (1966) Dish, 214-221) The content of cellulase in the cleaning composition of the present invention is such that the cellulase has an enzyme activity of 100 units/g or more, preferably 500 units/g or more, of bacteria and/or fungi. The amount of the original cellulase is such that the enzyme activity at the optimum pH is at least 100 units, preferably 500 units or more per 1 kg of the composition.

The method for measuring cellulase enzyme activity on cotton cloth is to use 200 mg of cotton cloth (with a degree of polymerization of at least 1000 obtained by the viscosity method and a cellulose type crystal structure obtained by the X-ray method) that has been shredded until stirring becomes easy; 10 mg of cellulase sample and optimum p showing maximum activity of each cellulase
A test bath consisting of 10 cc of an aqueous buffer solution containing H was heated at 40°C.
After mixing and stirring for 20 hours, the reducing sugars released are treated with DNS.
1 g of cellulase sample is 1 μm per minute.
One unit is the activity of producing a mole of reducing sugar.

The DNS method is a method in which the color produced when 3,5-dinitrosalicylic acid reacts with the reducing group of sugars under boiling conditions in alkaline conditions is compared (for details, see Sakuzo Fukui's [Biochemistry Experimental Methods!] Quantitative Method] P19. Published by Gakkai Publishing Center in 1969).

In the above measurement method, the optimum pH means the pH range in which each cellulase should exhibit its maximum activity.

The effects of the present invention are exhibited even when the quaternary ammonium salt powder is combined with any commonly used anionic surfactant, but in particular, as the anionic surfactant, C5° to C16 alkylbenzene sulfonate, C.I.
. ~C2゜olefin sulfonate, C1゜~CZO alkyl or alkenyl ethoxy (EO=0.5-8)
Good results can be obtained when one or more of sulfates, C0°-C2° alkyl or fluorenyl sulfates are used.

In addition, the composition of the present invention may contain the following components commonly used in detergents.

Ampholytic surfactants include carboxy or sulfobetaine type surfactants, nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers,
Examples include polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid ester, fatty acid glycerol heptanoester, and alkylamine oxide.

Other auxiliary additives include phosphates such as aluminosilicates, tripolyhydrochlorides, and pyrophosphates, salts of ethane-1,1-diphosphonic acid, and phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid. acid salt, aspartic acid,
Salts of amino acids such as glutamic acid, aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate, polymer electrolytes such as polyacrylic acid and polyaconitic acid, non-dissociated polymers such as polyvinyl alcohol and polyvinylpyrrolidone, diglycolic acid Builders and divalent metal ion scavengers such as salts of organic acids such as , oxycarboxylate, and phosphate; alkaline agents such as silicates, carbonates, and sulfates; or inorganic electrolytes; recontamination inhibitors such as polyvinylpyrrolidone and carboxymethyl cellulose; , enzymes such as alcalase, lipase, anti-caking agents such as para-toluene sulfonate, sulfosuccinate, talc, calcium silicate,
Bleach agents such as sodium percarbonate, sodium perborate or tetrahydrate, bleach activators such as triacetyl cyanurate, sodium p-acetoxybenzenesulfonate,
Peroxide stabilizers such as magnesium silicate and magnesium sulfate, antioxidants such as tert-butylated hydroxytoluene and gistyrenated cresol, fluorescent dyes, blue tinting agents,
It may contain fragrances and the like, but this is not particularly limited and may be blended depending on the purpose.

There are no particular restrictions on the mixing/blending method used in the present invention. For example, quaternary ammonium salt powder particles obtained by a spray cooling method or extrusion granulation method are quantitatively dropped from a hopper or belt onto a detergent material that is constantly transferred, or into a mixer such as a rotary kiln. A method is used in which a predetermined amount of detergent material and quaternary ammonium salt powder particles are added and mixed.

The detergent dough used in the present invention may be manufactured by a known manufacturing method such as spray drying or granulation, and detergent dough manufactured by the spray drying method is preferably used. The cleaning material produced by the spray drying method is produced by spraying an aqueous slurry of heat-resistant components such as surfactants and builders into a heated space and drying it, without any particular restrictions on the manufacturing conditions.
They are hollow particles with a size of 0 to 700 μm, and components such as fragrances, enzymes, bleaching agents, and inorganic alkali builders such as zeolite and soda carbonate may be added after the spray drying.

〔Effect of the invention〕

The detergent composition of the present invention thus obtained has an extremely small amount of anionic surfactant that is wasted as it is consumed by the quaternary ammonium salt, and furthermore has excellent cleaning properties due to the interaction with cellulase. It provides strength and at the same time gives clothes excellent flexibility and hygroscopicity, and the quaternary ammonium salt adsorbed and remaining on the washed fabric also exhibits excellent foam removal properties during rinsing.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Table 1 of this example shows that the finishing effect of the product of the present invention on cotton knitted underwear and the cleaning effect on natural collar fabric are extremely large.

(1) Detergent fabric (spray heat dried detergent fabric) Straight chain alkyl (τ12) benzene 19% by weight Sodium sulfonate Sodium tallow alkyl fatty acid 15TPP<I
- Sodium lipolyphosphate > 17 weight synthetic zeolite 2 JIS No. 2 sodium silicate 10 Sodium carbonate
5 Carboxymethylcellulose 1 Fluorescent dye Trace amount of fragrance
Trace water 5 Glauber's salt Balance (2) Cellulase used 2% of the following cellulase was blended (after blend) into the detergent fabric having the composition shown in (1).

A Cellulase (SIGMA, Type I, origin Asper5i
11usniger) B Alkaline cellulase (chemical soap, fiBacillus sp,, Microtechnical Research Institute No. 1138, 16,900 HU/g-sol
id)% 3) Quaternary ammonium salt used Dialkyldimethylammonium methosulfate CC+11/Cl having various crystal forms measured by the methods shown below.
6=53.6/46.4 (weight ratio) or C1fi/C
l6 = 10010 (weight ratio), both viscosity is 149 ~
350μ (average particle size: 250μ)] was blended at 1.5% (after blend) into the detergent fabric having the composition shown in (1).

The first-order diffraction peak intensity (1) of the long side spacing and the maximum peak intensity (n) of the side spacing were measured by the following method.

A sample was uniformly pressed into a glass cell for X-ray measurement, and an X-ray diffraction spectrum was measured under the following conditions.

First-order diffraction peak height of long-plane spacing (2θ-3,10')
and maximum peak height of side spacing (2θ=21.7')
was measured from the baseline and the intensity ratio (I) shown in Table 1
/ (II) was obtained.

(4) Flexibility evaluation Washing treatment conditions Using a commercially available electric washing machine, add 0.0% detergent to 20°C tap water.
13%, bath ratio 1. The cotton knitted underwear was washed under the condition of okg/30β, rinsed, dehydrated, and air-dried to be evaluated for sensory flexibility by a panel of 20 female specialists for evaluation of softness effects.

(5) Cleaning power evaluation i) Natural collar cloth contaminated cloth Cotton Imaichi #2023 cloth was sewn onto the collar of a dress shirt.
Have an adult male wear it for 3 days. 25℃, 65%R after wearing
After leaving it in H for one month, the degree of staining was divided into three levels, and from among the most heavily soiled fabrics, the fabric with the stains symmetrical about the center line was selected, and the fabric was cut in half at the symmetrical point of the stains and used for experiments. did.

ii) Cleaning conditions and method When cleaning naturally contaminated cloth, cut a 9 cm x 30 cm naturally contaminated cloth in half at symmetrical positions, and cut the 9 cm x 15 cm
One of the pair of contaminated cloths was washed with Cellulanize additive-free detergent, which is a standard detergent, and the other was washed with the detergent of the present invention, which is a comparative detergent. First, buy 15 pieces of naturally contaminated cloth for 50c.
Sewn on m x 50cm cotton cloth, 0.665% of 6i
A total of 1 kg of this contaminated cloth and cotton underwear is added to the detergent solution of
After soaking at 30° C. for 2 hours, the sample was transferred to a washing machine manufactured by Toshiba "Ginga", the total volume was adjusted to 301, washed for 10 minutes with strong inversion, and after drying, it was subjected to evaluation.

A half-cut fabric washed with the standard detergent and a half-cut fabric washed with the detergent of the present invention were evaluated by pairwise comparison by visual judgment. Based on standard stains ranked in 10 stages to indicate the degree of stains,
The cleaning cloths were ranked. The detergency was expressed as a score for the detergency of the detergent of the present invention, with the detergency of the reference detergent set at 100. A difference in detergency index of 0.5 or more can be considered a significant difference.

Example 2 Table 2 of this example shows that the finishing effect of the product of the present invention on cotton knitted underwear, the cleaning effect of the product of the present invention on natural collar stains, and the improvement in the water absorbency of cotton towels are extremely significant.

(Enzymes used) A Cellulase (SIGMA, Type I, Origin to spergi)
B. Alkaline cellulase (Bacillus sp., 9mm) C. Protease (Novo Industries, Alcalase 2.0M) D. Amylase (Novo Industries, Termamil 60G) E. Lipase (Novo Industries, Inc.) company, 5P-285) (1)
Finishing effect and verification method on cotton knitted underwear Detergent fabric: Composition obtained by removing protease from the fabric of Example 1 Enzyme: 2% of the above enzyme was blended into the detergent fabric (after blend).

Quaternary ammonium salt: 1.5% dialkyldimethylammonium methosulfate having the intensity ratio (r)/(II) shown in Table 3 measured in the same manner as Example 1 was added to the detergent fabric (after blending) )did.

Cleaning conditions: Same as Example 1 (2) Method for verifying cleaning effect on natural collar stains Cleaning agent Fabric, enzyme, quaternary ammonium: Same as (1) Natural collar stains, cleaning conditions and method ...Same as Example 1 (3) Washing treatment conditions and water absorption test Using a commercially available electric washing machine, 0.13% detergent and bath ratio 1 were added to tap water at 20°C.
．． Commercially available cotton towels were washed under Okg/30β conditions, rinsed, dehydrated, air-dried, and then heated at 25°C and 65°C.
It was left in a constant temperature and humidity room at %RH for 24 hours. This cotton towel was cut into a strip of 3 cm x 20 cm, one end of which was 2 cm soaked in water, and the height of the water rise after 15 minutes was measured.

Proceedings Written by the principal author (spontaneous) August 30, 1985 1. Indication of the case Japanese Patent Application No. 146111/1982 2. Name of the invention Detergent composition 3. Person making the amendment Relationship to the case Patent applicant (091) Kao Soap Co., Ltd. 4, Agent 1, Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo, 3 Nakai Building Specification Column 6 Detailed Description of the Invention, Contents of Amendment

Claims (1)

[Scope of Claims] 1. Powder-like detergent material containing an anionic surfactant contains cellulase of bacterial or fungal origin, and general formula (1) ▲Mathematical formula, chemical formula, table, etc.▼(1) (In the formula, R_1 and R_2 are C_1_0 to C_2_2 alkyl or alkenyl groups, R_3 and R_4 are lower alkyl groups, X is CH_3SO_4, C_2H_5S
O_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or indicates a halogen element), and is expressed as the first-order diffraction peak intensity (I) of the long side spacing and the maximum peak intensity (II) of the side spacing in X-ray diffraction. A cleaning composition comprising powder particles of a quaternary ammonium salt having a ratio (I)/(II) of 2.0 or less. 2. The cleaning composition according to claim 1, wherein the cellulase is an alkaline cellulase that retains sufficient activity even in alkaline conditions.