JPS61276897A - 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 Application Field] The present invention provides a detergent that can be used in laundry work to provide high detergency performance as well as excellent hygroscopicity and flexibility to clothing. Regarding the composition.

[Conventional technology]

Conventionally, detergent compositions containing anionic surfactants as the main ingredient have been widely used for washing clothes, but clothes washed with such detergent compositions have a rough texture. This tendency was remarkable in the case of clothes that were washed repeatedly at a density of 1%. Therefore, in general, after washing, a fabric softener called a softener is often used to perform treatments such as softening and antistatic treatment.

In recent years, this cleaning and finishing treatment has become more important! In order to save time and effort, cleaning compositions have been developed that perform cleaning and finishing treatments at the same time. However, since these products on the market use cationic surfactants for the purpose of imparting effects such as soft finishing and antistatic treatment, there is no interaction with anionic surfactants, which are the main components of cleaning compositions. However, simply mixing the two components does not fully achieve the desired effect, and various improvements have been made.

The present inventors conducted various studies regarding the physical properties of quaternary ammonium salts, and found that certain quaternary ammonium salts act as anionic surfactants even when incorporated alone in cleaning compositions. When attacked by
-68400).

[Problem that the invention seeks to solve]

By the above-mentioned technique, it was possible to obtain a detergent composition that imparts excellent flexibility to clothing.

However, among clothing, underwear, towels, etc. are required to have not only flexibility but also water absorbency, and further study was required.

The softening effect of the 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 that it makes clothing water repellent and reduces water absorption.

[Means for solving problems]

The present inventors have carried out intensive studies to compensate for the water absorption properties of cleaning compositions containing 48th ammonium salts, which have the above-mentioned contradictory properties. The present inventors have discovered that by blending cellulase, which is 1% with cellulose, it is possible to impart excellent water absorption to cellulose fibers such as cotton, and surprisingly, the softening effect is also significantly improved, and the present invention has been completed. .

That is, one aspect of the present invention is to add cellulase (% alkaline cellulase) and the following formula (I) or (I) to a powdery detergent material containing an anionic surfactant.

(In the formula, R1 and R2 are C1°SC2□ alkyl or alkenyl groups, and R5 and R4 are lower alkyl groups.

The present invention provides a cleaning composition characterized in that it contains powder particles of a quaternary ammonium salt represented by the following formula (R represents a lower alkyl group).

The quaternary ammonium salt of formula (II) or (II) used in the present invention is a known compound and can be prepared by a conventional method. The method described in JP-A-59-68400 is preferable.

As the powder particles of the quaternary ammonium salt.

If the average particle size is 1005550μ, it is substantially 50μ
It is preferable to use particles that do not contain particles of 0μ or more.If the particle size is too small, the surface area of the particles becomes large, making them susceptible to the action of anionic activators. The drawback is that particles that fall off or adhere to clothing are noticeable.

(9) The apparent specific gravity of the powder particles of the quaternary ammonium salt should be at least 0.25, and preferably at least 0.4.

The tJcA class ammonium salt powder 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
Preferably it is 25%.

The effects of the present invention are exhibited even when the quaternary ammonium salt powder is combined with any of the commonly used anionic surfactants, but in particular, as anionic surfactants, the following (,) average carbon number: 10 - a-chain or branched alkylbenzene sulfonate (+) having 16 alkyl groups; having an average of 10 to 20 straight-chain or branched-chain alkyl or alkenyl groups, with an average of 0 carbon atoms per molecule; Alkyl or alkenyl ethoxy sulfate with 5 to 8 moles of ethylene oxide added (0) Alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms (d) An average of 10 to 20 carbon atoms t - using one or more types of olefin sulfonates in one molecule (the counter ions of these anionic surfactants are alkali metal ions, alkaline earth metal ions, ammonium ions, or alkanolamines); If you do, you will get good results.

Further, as an example of blending a quaternary ammonium salt and an anionic surfactant to obtain particularly good results, the total weight ratio of the anionic surfactant and the quaternary ammonium salt is 5:IA-50. :1, and the total weight ratio of the anionic surfactants other than (a) to the quaternary ammonium salt is 10:1 or less, and (0) and the quaternary ammonium salt Examples include the case where the weight ratio is 3=1 or less.

Cellulase, which is one of the essential components of the present invention, includes animals and plants, I
im bacteria, those widely distributed among fungi, and purified fractions thereof can be used, 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, by using an alkaline cellulase that retains sufficient activity even in alkaline conditions, especially an alkaline cellulase of bacterial origin, a higher finish and cleaning effect can be obtained. Examples of alkaline cellulases include the following.

(IL) Cellulase cultured and collected from a bacterium belonging to the genus Aeromonas whose microbial deposit number is Microorganism Research Institute No. 2506 (see JP-A-50-76287) (b) Microorganism deposit number is Microorganism Research Institute No. 2506 Submission No. 1158.

No. 1159, No. 1140 and No. 1141 Cellulases collected from cultured bacteria belonging to Bacillus N4 (see Japanese Patent Publication No. 50-28515 M
) (C) Snail; Trapela aurioula solander (Dolaballa &urioula 5o
Cellulase originating from the midgut gland extract of P. lander (Bio-Oh8m, J., (II966) 99, 21
45221) The present invention can use, for example, the following commercially available cellulases using these various sources.

(II) Cellulase A
P) Amano Pharmaceutical Co., Ltd. (2) Cellulosin AP (
Celluloain AP) Ueda Chemical Co., Ltd., (
3) Cellu-1osin AC
) Ueda Chemical Co., Ltd., (4) Cellular See Onozuka (C
ellulase-Onozuka) Kinki Yakult Manufacturing Co., Ltd., (5) Bancellase (Panoellaae
) Kinki Yakult Sakuzo Co., Ltd., (6) Mashichi Rozyme (M
aoarozyme) Kinki Yakult Manufacturing Co., Ltd., ()
) Meicalaae Meiji Seika Co., Ltd.

(8) Cellzyme (Gelluzym Nagase Co., Ltd.,
(91 Solubl sucrase (Solulu gcl)
aaa) Sankyo Co., Ltd., AL Sanzy
me) Sankyo Co., Ltd., an cellulase A-12-C (C
ellulase A-12-0) Takeda Pharmaceutical Co., Ltd., Q2) -Toyo-Cellulase (Toyo-Cellu
lase) Toyo Jozo Co., Ltd., Fukan Driselase (
Driserase) Kyowa Hakko Kogyo Co., Ltd., fi4 Luizyme) Louisboldt Berg Co., Ltd. (L
uipoldwork), a9 Takamine-Oellulaae Chemische Fabr.
ik), (II8 Wallergtein-Cellulase) Sigma Chemicals (81gma Chemicals)
, Qfi cellulase e type 1 (Oallulas
a Type 1) Sigma Chemicals Co., Ltd.
a Ohemiaalg), α-second cellulase selva (
Cellulase 8srva) Serva Laboratory, (I
I9 Cellulase 36 (Cellulase 56)
Rohm and Haa
s), (2G-v virus φ cellulase 4.000
(Miles Ce1lulase 4,000) Milea, e! Il RAM
Cellulase 55.36. ! i8: r link (RAM C
e1lulase 35,56.5130ONO) Philip Morris Co., Ltd.
123 =ry Gombizym Nysoo Laborazor
y), a! 1 Cellulase (Oellulase) Makor Chemicals
ss).

Collucruat (Foundation) Novo Induazry
, @Cellulage Giat-Brooades The content of cellulase in the cleaning composition of the present invention is determined by cellulase having an enzyme activity of 100 units/g or more, preferably 500 units/g or more of cellulase on cotton cloth, or / and cellulase of fungal origin with an enzyme activity of at least 100 units, preferably 50 units per kg of the composition.
It is a lid that has 0 units or more.

The method for measuring the enzyme activity of cellulase on cotton cloth is to cut the cotton cloth until it is easily stirred (the degree of polymerization obtained by the viscosity method is at least 1000 and the crystal structure obtained by the X-ray method is cellulose! type).200In9 ．． 10 cellulase samples and optimal p showing maximum activity of each cellulase
A test bath consisting of an aqueous buffer solution containing H and 10α was heated at 40°C.
The reducing sugar released after mixing and stirring for 20 hours was measured using the DNS method, and the IJ cellulase sample was measured at a rate of 1 m^n1 per minute.
One unit is the activity of ole to produce reducing sugars.

The DNS method is a method that compares the color produced when 3.5 dinitrosalicylic acid reacts with reducing groups of sugars under boiling conditions in alkaline conditions.
, ``Method for Determination of Reducing Sugars'' PI3.1969, published by Gakkai Publishing Center).

In the above measurement method, "optimal" means a range in which each cellulase should exhibit its maximum activity.

There are no particular restrictions on the mixing/blending method used in the present invention. For example, quaternary ammonium salt powder particles and hiscellulase obtained by a spray cooling method or an extrusion granulation method are dropped onto a regularly transferred detergent material onto a hopper, a belt, or a rotary kiln. A method is used in which a predetermined amount of detergent material, quaternary ammonium salt powder particles, and cellulase are placed in a mixer and mixed.

The detergent material used in the present invention may be manufactured by a known manufacturing method such as a spray drying method or a forming method, and a detergent material manufactured by a spray drying method is preferably used. There are no particular restrictions on the manufacturing conditions for the cleaning material manufactured by the spray drying method, and the particle size obtained by spraying an aqueous slurry of heat-resistant components such as surfactants and builders into a heated space and drying it is within the range of approximately 50 to 700 μm. In the form of granules, components such as fragrances, enzymes, bleaching agents, and inorganic alkali builders such as zeolite and soda carbonate may be added after the spray drying.

In addition to the above-mentioned essential components, the cleaning composition of the present invention contains various components that are included in general cleaning agents.

For example, the following components can be optionally blended.

(II) Nonionic surfactant polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, high a
nh Fatty acid alkanolamide or its alkylene oxide adduct, etc.

(2) One or more of various builder or primary alkali metal salts may be contained in an amount of 0 to 50% as a builder component. Condensed phosphates such as tripolyphosphate, birophosphate, metaphosphate, aminopolyacetate such as nitrilotriacetate, ethylenecyabanetetraacetate, diethylenetriaminepentaacetate, citrate, malate, glycol Oxycarboxylic acid salts such as acid salts, polyacrylic acid and its salts, alkaline hydrolyzed salts of vinyl acetate-maleic anhydride copolymer-1
Polymer electrolytes such as polyacetal carboxylate polymers described in JP-A-54-52196.

Further water-insoluble substances include Merck, finely powdered silica, clay, calcium silicate, crystalline and/or amorphous aluminosilicate.

(3) Alkaline agent or inorganic electrolyte Furthermore, the composition contains 0 to 50% by weight, preferably 5 to 50% by weight of one or more of various alkali metal salts of the following as an alkaline agent or inorganic electrolyte. be able to. Silicates, carbonates, sulfates, and also as an organic alkaline agent, triethanolamine.

Jetanol azene, monoethanolamine.

It can also contain alkanolamines such as tri-inglopanolamine.

(4) Re-staining preventive agent The composition may further contain one or more of the following compounds as a re-staining preventive agent in an amount of 0.1 to 5%.

Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxylic dimethylcellulose, etc.

(5) Bleach, fluorescent dyes, enzymes, etc. Bleaching agents such as sodium percarbonate, sodium percarbonate, sodium sulfate, sodium chloride and hydrogen peroxide adducts, and commercially available fluorescent dyes as brighteners, fragrances, Enzymes such as protease, amylase, and lipase, as well as a blue tint agent, can also be added as necessary.

(6) Agents for inhibiting factors that inhibit cellulase activity Copper, zinc, chromium, mercury, lead, manganese.

Cellulase activity may be inactivated by the presence of ions and compounds such as silver. Examples of these metal ion scavengers include magnesium silicate, i-gnesium sulfate, and the like.

(7) Cellulase activator Protein, depending on the type of cellulase.

Cobalt and its salts, calcium and its salts.

Potassium and its salts, sodium and its salts.

When monosaccharides such as mannose and xylose coexist, cellulase is activated, and the cleaning effect and softening/moisture absorption effect are dramatically improved.

In addition, anti-caking agents, antioxidants, solubilizers, etc. may also be added as necessary.

〔Effect of the invention〕

The thus obtained cleaning composition of the present invention is as follows.

Very little amount of anionic surfactant is wasted as it is consumed by the quaternary ammonium salt.

Furthermore, due to its synergistic effect with cellulase, it provides excellent cleaning power during washing, and at the same time gives clothes excellent flexibility and hygroscopicity, and also absorbs into the fabric being washed.

It is also excellent in that it exhibits excellent foam removal properties during rinsing due to the action of the remaining quaternary ammonium salt.

〔Example〕

Next, the present invention will be specifically explained with reference to examples. An example of producing quaternary ammonium salt powder particles by a cooling solidification pulverization method is shown as a reference example.

Reference Example By adding 2 t% of water to a raw material solution of 90% quaternary ammonium salt, 9% inpropyl alcohol, and 1% water, the melting point of the quaternary ammonium salt mass increased by 10 to 2.
0°C lower temperature, i.e. the melting point of distearyldimethylammonium methosulfate 140°C #) 10 to 20
Desolvation operation was performed at 120-130°C.

The desolvated quaternary ammonium salt is sequentially cooled and solidified while being kneaded in a continuous kneader cooler through which cooling water is passed.
A lump of about 10 cm was obtained at 5 to 20°C and firstly pulverized using a pulverizer. Thereafter, the particles were classified to have a desired particle size.

(In addition, the mixed granules with other ingredients as a comparison sample are
By adding and mixing other components to the molten quaternary ammonium salt that was desolvated in the above reference example, powder particles were prepared according to the above reference example. ) The obtained quaternary ammonium salt powder particles had a moisture content of 0.2% and an apparent specific gravity of 0.45.

Example 1 This example shows that the finishing effect of the product of the present invention on cotton knitted underwear is extremely large.

(II) Detergent fabric (detergent fabric dried by spray heat) Okin process alkyl (01 Sodium sulfate 5 Sodium tallow alkyl fatty acid 1 Synthetic zeolite 2 JI No. 32 Sodium silicate 10 Sodium carbonate 5 Carboxymethyl cellulose 1 Fluorescent dye
trace fragrance
l Moisture
5 pieces of glass
Balance (2) 2% of the following cellulase was blended (after blended) into the detergent fabric with the composition shown in the used cellulase (II) (3) The composition shown in the used quaternary ammonium salt (II) Particle size T-149 to 35 was added to the detergent fabric by the reference manufacturing method.
0μ (average paddy diameter t-250μ) as shown in Table 1.
Grade ammonium salt powder particles (, ) or mixed granules of quaternary ammonium salt and other components (II)) 1゜4th
1.5% of grade ammonium base line was blended (after blended).

(4) Cleaning treatment conditions Using a commercially available electric washing machine, add 0.0% cleaning agent to 20°C tap water.
13%, bath ratio 1. Cotton knitted underwear was washed under the conditions of Oky/SG 4, rinsed, dehydrated and air-dried, and then subjected to evaluation of sensory flexibility by a panel of 20 female specialists for evaluation of softness effects.

The above test results are shown in Table 82.

Table 2 Quaternary ammonium salt Cellulase Flexibility
2 Table (continued) Table 2 (continued) Quaternary ammonium salt Cellulase Flexibility No. 2
Table Continued Quaternary ammonium salt Cellulase The main effect values of the modified flexibility method are shown.

Example 2 This example demonstrates 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 stains, and the improvement in the water absorbency of cotton towels after treatment with the product of the present invention are extremely significant. show.

(Nine enzymes used) ■ Cellulase (SIGMA, 'rypat, origin: Aspergillus+sniger) ■ Alkaline cellulase (dead weight, origin: Bacillus sp.
.

Microtechnology Kenzonoyori No. 1138) ■Protease (Novo Industries, Inc.)

Alcalase 2. OM) ■Amylase (Novo Industries, Inc.)

Terma Mill 60G) ■Lipase (Novo Industries, Inc.)

19P-285) (Quaternary ammonium salt used) A Distearyldimethylammonium methosulfate B Dipalbutyldimethylammonium methosulfate (Tertiary amine used) O Citaloylmethylamine D Distearylmethylamine (II) Cotton Method for verifying finishing effect on knitted underwear Cleaning fabric: Composition of fabric from Example 1 with protease removed Enzyme: 2% of the above enzyme added to cleaning fabric (
After blending) quaternary ammonium salts and tertiary amines.

... 1.5% pure content was added to the detergent fabric (after blend).

Cleaning treatment conditions: Same as Example 1 (2) Method for verifying cleaning effect on natural collar stains Cleaning agent fabric, enzyme, quaternary ammonium salt, and No. 37 ban...
・Similar to +1) Natural rubbing cloth contaminated cloth, washing conditions and method Natural collar cloth contaminated cloth Cotton gold #202S cloth was sewn onto the collar of a dress shirt and an adult male was allowed to wear it for 5 days. 25℃, 65%RH after wearing
After being left for one month, the degree of staining was divided into three levels, and from among the most heavily soiled fabrics, the fabric with stains symmetrical to the center was selected and cut in half at the symmetrical point of staining for use in experiments. .

Cleaning Conditions and Methods When cleaning naturally contaminated cloth, cut 91) lx50aa naturally contaminated cloth in half at symmetrical positions. (To) x 15QIB One of a pair of contaminated cloths was washed with a cellulase-free detergent, which was a reference detergent, and one was washed with a detergent of the present invention, which was a comparative detergent. First, 15 pieces of naturally contaminated cloth are worth 500 II.
Sewn onto X501 cotton cloth, put 1 kg of the contaminated cloth and cotton underwear in 6 bottles of 0.665% detergent solution, soaked at 30℃ for 2 hours, and then transferred to Toshiba washing machine "Galaxy". , after setting the total il to 50 no.

It was washed with strong inversion for 10 minutes, dried, and then 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. Ranked in 10 stages to express the degree of dirt, based on nine standard dirts,
The cleaning cloths were ranked. The cleaning performance is based on the cleaning power of the standard detergent.
It was expressed as a score of detergency of uninvented and bright detergents when set to -100. A difference in detergency index of 0.5 or more can be considered a significant difference.

(3) Cotton towel water absorption test Cleaning agent fabric, enzyme, quaternary ammonium salt, and tertiary amine...Same washing treatment conditions and water absorption test as in (II)...Using a commercially available electric washing machine, Detergent 0.13% in tap water at ℃, bath ratio 1. A commercially available cotton towel was washed under the conditions of Okl/50, rinsed, dehydrated, air dried, and placed in a constant temperature and humidity room at 25° C. and 65% RH for several hours. Cut this cotton towel into 3x2001 strips and soak one end in 2Qm water.

Measure the height of water rise after 15 minutes. Established.

The above test results are shown in Table 3.

Claims (1)

[Claims] 1. Cellulase and the following formula (I) or (II) ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 and R_2 are alkyl or alkenyl of C_1_0 to C_2_2, R_3 and R_4 are lower alkyl groups, 1 represents a lower alkyl group.) A cleaning composition characterized in that it contains powder particles of a quaternary ammonium salt represented by the following. 2. The cleaning composition according to claim 1, wherein the cellulase is an alkaline cellulase that retains sufficient activity even in alkaline conditions.