JP2597335B2 - Detergent composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a detergent composition capable of imparting a softening effect to clothing simultaneously with washing.

2. Description of the Related Art Generally, when washing clothes at home to impart flexibility, the detergent components are rinsed with a large amount of water after washing with a detergent, and then a cationic surfactant such as a quaternary ammonium salt is used as a main component. And a method of treating by adding a softening agent.

This is because the cationic surfactant has an excellent softening effect and an antistatic effect, but cannot provide a sufficient softening effect when used together with a detergent. This is because home detergents generally contain an anionic surfactant as a main component, so the anionic surfactant in the detergent is attacked by the anionic surfactant in the detergent before the cationic surfactant is adsorbed on clothing, This is because the dispersion is stabilized and becomes less likely to be adsorbed on clothing.

However, separately performing washing and soft finishing requires extra time and labor, and consumers have demanded a detergent having both washing and soft finishing.

To solve this problem, JP-A-59-6293 (use of non-ionic cellulose), JP-A-59-6294 (use of alkylamine), and JP-A-59-6295 (mono or diglyceride) The use of cationic surfactants after some treatment has been reported, and granulation with zeolite and granulation with polyethylene glycol or nonionic surfactants are known. I have.

The present applicant has previously proposed to improve the flexibility-imparting effect by using specific high bulk density detergent particles and cationic surfactant particles (Japanese Patent Application Laid-Open No. 61-314630).
issue).

Furthermore, Japanese Patent Publication No. 56-21795 reports that smectite clay is used as a softening agent.

It is also known that bentonite has a softening effect on cotton cloth, and it is also known that the softening effect can be improved by using bentonite having a hydroxyl value of 25 or more (JP-A-56-72094). Gazette).

However, further improvement has been awaited in terms of the effect of imparting flexibility.

Problems to be Solved by the Invention The present invention provides a detergent composition that can impart even more excellent flexibility to fibers after washing.

The cleaning composition of the present invention contains the following components (a), (b) and (c), and the weight ratio of the components (a) and (b) is (a) / ( b) = 50/1 to 5/1.

(A) Anionic surfactant: 20 to 50% by weight.

(B) A cationic surfactant represented by the general formula (I).

(Each symbol in the formula is as follows.

R ₁ , R ₂ : C _{12 to} C ₂₆ alkyl or alkenyl R ₃ , R ₄ : C _{1 to} C ₄ alkyl, benzyl, C _{2 to} C ₄ hydroxyalkyl or polyoxyalkylene X : Halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1 / 2SO ₄ , or (C) Alkaline lipase having a lipase activity at pH 7 of 30% or more of the lipase activity at pH 7.

 Hereinafter, the present invention will be described in more detail.

Specific examples of the anionic surfactant (a) include:
The following can be exemplified.

1) linear alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms; 2) olefin sulfonate having an average of 10 to 20 carbon atoms; 3) alkyl sulfate having an average of 10 to 20 carbon atoms; 4) average Alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and having an average of 0.5 to 8 moles of ethylene oxide added thereto; 5) a compound represented by the following general formula: Α-sulfofatty acid salt or α-sulfofatty acid ester salt to be used.

(Wherein Y is an alkyl group or counter ion having 1 to 3 carbon atoms, Z is a counter ion, and R is an alkyl group or alkenyl group having 10 to 22 carbon atoms.) As a counter ion in these anionic surfactants Can be sodium, potassium, ethanolamine, ammonium and the like.

The anionic surfactant (a) is incorporated in the detergent composition of the present invention in an amount of 20 to 50% by weight, preferably 30 to 50% by weight. If the amount is less than 20% by weight, the detergency is insufficient, while if it exceeds 50% by weight, the production becomes difficult.

Specific examples of the (b) component anionic surfactant include:
For example, the following may be mentioned, and specific examples of the counter ion include chloride and bromide.

1) distearyldimethylammonium salt, 2) dihydrogenated tallow alkyldimethylammonium salt, 3) dihydrogenated tallowalkylmethylbenzylammonium salt, 4) distearylmethylbenzylammonium salt, 5) distearylmethylhydroxyethylammonium salt, 6) Distearyl methyl hydroxypropyl ammonium salt; 7) Distearyl dihydroxyethyl ammonium salt; 8) Dioleyl dimethyl ammonium salt.

(B) The cationic surfactant is usually produced in a state in which a solvent such as isopropyl alcohol is added, and the solvent is removed therefrom to obtain 90 to 98% as a pure component and an average particle size of 10 to 50.
It is desirable to use a powder of 0 μm, granulated together with an inorganic or organic compound. By performing such a treatment, it is possible to enhance the softening effect and improve the powder characteristics when used in combination with the anionic surfactant. As these compounds, non-ionic cellulose such as methyl cellulose, acrylamide polymer,
Zeolite, polyethylene glycol, polyoxyalkylene alkyl ether and the like can be mentioned.

As the alkaline lipase of the component (c), those having a lipase activity at pH = 9 of 30% or more, preferably 50% or more, of the lipase activity at pH = 7 are used.

The lipase activity at pH 7 and pH 9 can be measured as follows.

*) Lipase activity measurement method Using olive oil as a substrate, the fatty acid released by the lipase action is quantified by alkali titration, and the lipase activity is determined from the numerical value.

As an enzyme unit, one unit is defined as an enzyme that releases 1 μM fatty acid per minute from olive oil substrate at 37 ° C.

4 ml of olive oil emulsion and 4 ml of 0.1 M phosphate buffer (pH 7.0)
Is placed in a 50-ml stoppered Erlenmeyer flask, mixed well, and preheated for 10 minutes in a thermostatic water bath at 37 ° C. To this, add exactly 1 ml of the sample solution, mix well, and after exactly 20 minutes, titrate with a mixture of acetone and ethanol.

Separately, 5 ml of olive oil emulsion and 0.1 M phosphate buffer (pH 7.
0) Accurately transfer 4 ml to a 50 ml conical Erlenmeyer flask
After heating at 30 ° C. for 30 minutes, the mixture is poured into 20 ml of a mixture of acetone and ethanol. Then, exactly 1 ml of the sample solution is added, and titrated with a 0.05N sodium hydroxide solution using 5 drops of a phenanolphthalene solution as an indicator to obtain a control solution.

Calculation of enzyme units In the measurement at pH = 9, the pH was adjusted to 9 using a 0.2 M Tris buffer, and the others were performed in accordance with the above method.

Lipases suitable for the present invention include Candida cylindra
cea, Humicola lanuginosa, Psudomonas, Mucor sp., Ch
There are microbial sources such as romobacterium viscosum and Rhizopus japonics, and lipase MY and lipase OF (
Akashi Sangyo Co., Ltd., origin Candida cylindracea), lipase P, lipase CES (above, Amano Pharmaceutical Co., Ltd., origin P)
seudomonas), Lipase SP (Novo, origin Mucor s)
p.), lipase (manufactured by Toyo Brewery Co., Ltd., origin Chromobacter
viscosum), lipase LPL (Oriental Yeast Co., Ltd.), oripase (Osaka Bacteria Research Institute, origin Rhiz)
opus japonics). JP-B-53-45394 discloses that a lipase-producing filamentous fungus belonging to the genus Humicola (including Thermomyces) is cultured and the lipase is collected from the culture; Langinosas S-38 strain (Microtechnical Laboratory No. 1045) has been reported, but such a lipase can also be used.

Furthermore, lipase produced from a genetically modified microorganism can also be used. One such example is disclosed in JP-A-62-2729.
No. 88 includes Aspergillus oryz
It has been reported that ae) is used as a host, transformed by recombinant DNA technology, and cultured in a culture medium to produce lipase.

(C) The amount of the alkaline lipase component is 1 kg of detergent.
It is preferable to mix in an amount of 10,000 to 1 million lipase units (LU) per unit.

Various optional components can be added to the cleaning composition of the present invention as needed. Optional components include other surfactants such as nonionic surfactants, zeolites, water-soluble phosphate-free calcium-trapping chelate builder; enzymes other than the alkaline lipase of the present invention; bleaching of sodium percarbonate, sodium perborate, etc. Agents, reducing agents such as sulfites, carboxymethylsemelose, anti-redeposition agents such as polyethylene glycol, soaps, optical brighteners, bentonite,
Flavors and the like can be used as needed.

As the zeolite, a crystalline or amorphous aluminosilicate represented by the following general formula (II) or a mixture thereof is preferable.

x (M ₂ O or M′O) · Al ₂ O ₃ · y (SiO ₂ ) · w (H
₂ O) (II) (wherein M is an alkali metal atom, M 'is an alkaline earth metal atom exchangeable with calcium, x, y and z represent the number of moles of each component. X is 0.7-1.
5, y is 1 to 3, and w is an arbitrary number. The average particle size of the zeolite is desirably 5 μm or less, preferably 1 μm or less from the viewpoint of detergency.

Examples of the water-soluble phosphorus-free calcium ion trapping builder include aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenetriaminepentaacetate; polyvalent carboxylate such as citrate; polyacrylic acid Salt, hydroxy polyacrylate, polyitaconate, polyacetal carboxylate, salt of copolymer of acrylic acid and maleic anhydride, salt of copolymer of maleic anhydride and methyl vinyl ether, maleic anhydride and olefin And a polymer electrolyte such as a salt of a copolymer of acrylic acid and methacrylic acid.

The above-mentioned chelate builders may be used alone or in combination of two or more.

As the enzyme, other enzymes such as protease, cellulase and amylase can be added in addition to the alkaline lipase of the present invention.

The detergent composition of the present invention can take various forms, for example, a hollow bead-like granular detergent like a conventional spray-dried detergent. Also, JP-A-60-96
As disclosed in Japanese Patent No. 698, a high bulk density granular detergent in which detergent components are filled inside the detergent particles can also be used.

When the detergent composition has a high bulk density, the bulk density is 0.5 to
The composition is preferably 1.2 g / cc, and such a composition is prepared by kneading each detergent component as described in, for example, JP-A-60-96698 and JP-A-62-597. Kneading,
After mixing, it can be produced by pulverizing and granulating with a cutter mill type pulverizer, and then coating with a water-insoluble fine powder. The detergent component can be supplied in the form of a spray-dried product and kneaded.

When a high bulk density detergent composition is used, it is preferable to use a nonionic surfactant.

The following are suitable as the nonionic surfactant.

(1) An EO-added nonionic surfactant obtained by adding an average of 7 to 30 mol of ethylene oxide (EO) to a primary or secondary alcohol having 8 to 18 carbon atoms.

(2) EO-PO addition type nonionic surface activity in which ethylene oxide (EO) is added to the primary or secondary alcohol having 8 to 18 carbon atoms in an average of 7 to 20 mol and propylene oxide (PO) in an average of 3 to 15 mol. Agent.

Although the components (a), (b) and (c) of the present invention can take various coexisting forms, the components (a), (b) and (c) are separately granulated together with other added components. Then, it is preferable to form a detergent composition by mixing detergent particles, cationic surfactant particles and lipase particles, respectively, and mixing these particles. (B) Cationic surfactant and (c) alkaline lipase can be granulated by a usual method.

Effects of the Invention According to the present invention, the flexibility imparting effect can be further improved by using a specific alkaline lipase and a cationic surfactant in combination to form a detergent composition.

Hereinafter, the present invention will be described more specifically with reference to examples. Prior to this, the evaluation method used in the examples will be described.

<Evaluation method of flexibility-imparting effect> An adult male was washed with a cationic surfactant and a detergent containing no enzyme (lipase) at 60 ° C for 15 minutes, and then rinsed three times at 60 ° C for 3 minutes. Wear for 2 days to make a flexible test cloth. Five skin shirts are cut in half, and a cotton knitted cloth is added to the cut to make 1 kg.

Next, the test cloth was placed in a jet-type household electric washing machine, and 30 l of tap water was added thereto. Then, 25 g of a test detergent composition was added thereto. The test cloth was washed at 25 ° C. for 10 minutes, dehydrated for 1 minute, and then dried at 25 ° C. The operation of rinsing with tap water for 3 minutes and then dehydrating for 1 minute was repeated twice. After that, air dry the test cloth for 24 hours, then 25 ℃
The air-dried test cloth was conditioned under conditions of 65% RH.

The skin shirt was taken out of the test cloth thus obtained, and the feel was evaluated by five judges, and the flexibility imparting effect of the detergent composition was evaluated from the average of the five judges. In addition, this touch determination was made to be zero for the touch of the skin shirt obtained by the same procedure as above except that the detergent composition containing no cationic surfactant and lipase was used, and a comparison with this was made according to the following criteria. Done.

Extremely soft 5 points Very soft 4 points Soft 3 points Slightly soft 2 points Slightly soft 1 point Example 1 (1) Preparation of detergent particles Nonionic surfactant was removed from the high bulk density detergent particles shown in Table 1 below. A detergent slurry having a solid content of 45% was prepared using each component. This detergent slurry was dried using a countercurrent spray drying tower at a hot air temperature of 380 ° C. to a water content of 5% to obtain a spray-dried product.

This spray-dried product has an average particle size of 350 μm and a bulk density of 0.35 g / c.
c, the angle of repose was 45 degrees and the fluidity was good.

Next, the dried product, nonionic surfactant and water were introduced into a continuous kneader (KRC Kneader # 2, manufactured by Kurimoto Tekkosho) to obtain a dense and uniform kneaded product.

A perforated plate (thickness: 10 mm) having 80 hole diameters of 5 mmφ was installed at the outlet of the kneader, and the kneaded product was formed into a cylindrical pellet of about 5 mmφ × 10 mm.

The pellets were introduced into a crusher (Speedmill ND-10, Okada Seiko Co., Ltd.) together with twice (weight ratio) cooling air at 15 ° C. At the same time, as a grinding aid,
Pulverized sodium carbonate (average particle size 30μm)
4 parts by weight were added to 100 parts by weight.

The crusher has a cutter with a length of 15 cm in four stages of cloth, rotates at 3000 rpm, and the screen is made of 360-degree punched metal. This crusher is connected in three stages continuously,
Hole diameter of each screen is 1st stage: 3.5mmφ, 2nd stage: 2mm
φ, third stage: 1.5 mmφ. After the particles having passed through the crusher in three stages are separated from the cooling air, zeolite having an average primary particle size of 1 μm is added to the pulverized material at 2% and coated. g / cc of detergent particles were obtained.

(2) Preparation of Cationic Surfactant Particles Dihydrogenated tallow alkyldimethylammonium chloride (Arcard 2HT, 93% pure) is melted at 120 ° C., and methylcellulose powder (1% against Arcard 2HT) is added, cooled, and then blocked. Glauber's salt powder (20% with respect to the block) is added to the mixture and pulverized to an average particle size of about 80 μm.

 The cationic particles contain 71% Arcard 2HT.

(3) Preparation of lipase particles 100 g of various lipases, 500 g of NaCl and 300 g of CaSO.2H ₂ O
And a 1% aqueous solution of carboxymethylcellulose 10
While adding 0 g, granulation was performed at 200 rpm using a mixing granulator LMA-10 (Nara Seisakusho). After the particles and dried 3% water in a fluidized bed, the PEG # 600 30 g, the TiO ₂ coated surface was added 50 g.

After cooling, the mixture is sieved and granulated at 250 to 1000 μm, with an average particle size of 5
00 μm lipase particles were obtained.

(4) Preparation of Detergent Composition (High Bulk Density) Detergent particles, cationic surfactant particles and lipase particles were powder-mixed in the ratio shown in Table 1 to prepare a detergent composition.

These were evaluated for flexibility, and the results are shown in the table.

Details of the components used in the table are shown below.

LAS-Na; linear alkylbenzene sulfonate having 10 to 14 carbon atoms in the alkyl group LAS-K; potassium linear alkylbenzene sulfonate having 10 to 14 carbon atoms in the alkyl group AOS-Na; C _14-18 α- Sodium olefin sulfonate AS-Na; C _12-14 alkyl sodium sulfate ester Nonionic surfactant I; C _12-13 EO of primary alcohol = 1
5 mol adduct Nonionic surfactant II; C _12-14 EO of secondary alcohol =
15 mol, PO = 10 mol adduct PEG; polyethylene glycol, M = 6000 zeolite; A-type synthetic zeolite (average particle size: 0.9 μm) Silicic acid-Na; Na ₂ O: SiO ₂ = 1: 2.2 Carbonic acid-Na; Na ₂ CO ₃ (reagent product) Carbonic acid-K; K ₂ CO ₃ (reagent product) Sulfite-Na; Na ₂ SO ₃ (reagent product) Protease; Savinase 4.0T (Novo) Lipase; Lipase P (Amano Pharmaceutical) Activity Ratio = 100% (pH9 / PH7) Lipase; Lipase produced from Humicola lanuginosa Activity ratio = 70% (pH9 / PH7) Lipase; Lipase AP (manufactured by Amano Pharmaceutical) Activity ratio = 20% (pH9 / PH7) Example 2 Detergent particles shown in Table 2 below were prepared by spray drying.

The powder was mixed with the same cationic surfactant particles and lipase particles as in Example 1 to prepare a detergent composition, and the effect of imparting flexibility was evaluated.

Further, 7% by weight of a bentonite particle produced as described below was added to Sample No. 4 of Example 2 to prepare a detergent composition, which was evaluated in the same manner. The application effect was shown.

(4) Production of Bentonite Particles After mixing 1 part by weight of white carbon with 3 parts by weight of bentonite (Volclay HPM20, manufactured by American Colloid Co.), an aqueous solution of magnesium sulfate of 20 to 50 wt% with respect to bentonite is added and mixed. At this time, the mixture is adjusted so that the amount of magnesium sulfate after mixing is 3 wt% with respect to bentonite. This is extruded to a diameter of 0.8 mm using an extrusion granulator. Then after drying in a dryer, using a crusher and a sieve length 1 ~
It is adjusted to about 3 mm to obtain granulated bentonite particles.

Claims (1)

(57) [Claims] (1) (a) anionic surfactant: 20 to 50% by weight
And (b) the general formula (I) (The symbols in the formula are as follows: R ₁ , R ₂ : C _{12 to} C ₂₆ alkyl group or alkenyl group R ₃ , R ₄ : C _{1 to} C ₄ alkyl group, benzyl group, C ₂ -C ₄ hydroxyalkyl group or a polyoxyalkylene group X: _{halogen, CH 3 SO 4, C 2} H 5 SO 4, 1 / 2SO 4 or, And (c) alkaline lipase having a lipase activity at pH 9 of 30% or more of the lipase activity at pH 7, and (a) / (b) = 50/1 to A cleaning composition characterized by being in the range of 5/1.