JP2800162B2 - Detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a cleaning composition which has low foaming during cleaning and has extremely good rinsing properties.

2. Description of the Related Art Conventionally, there has been a demand in Japan for clothing detergents to foam properly when washed. This is because consumers tended to judge the detergency of the detergent by the foam. But,
Foaming is a property of a detergent that is essentially separate from the cleaning power of the detergent.

2. Description of the Related Art In recent years, fully automatic washing machines have been rapidly spreading. Since the fully automatic washing machine is automatically operated according to a pre-programmed washing-rinsing-dehydration cycle, the consumer removes the washed clothes at the end after putting detergent and clothes into the washing machine. No other operation is required. Thus, the washing-rinsing process becomes a black box, and the tendency to adjust the amount of detergent or the amount of clothing using foam as an indicator of detergency diminishes, but rather to ensure that rinsing is completed within the programmed rinsing process. As a result, detergents having low foaming properties and good rinsing properties have been preferred.

In addition, with the upsizing and diversification of laundry by consumers and the increase in the number of employed housewives, fully automatic washing and drying machines that are completely automated from washing to drying are gradually spreading. Most of this type of washing machine employs a so-called drum type in which the rotation axis of the washing tub is parallel to the floor surface. A drum-type washing machine differs from a conventional pulsator type in that washing is performed by tapping and washing. Therefore, when foaming occurs during washing, the cloth to be washed becomes difficult to move in the washing tub, and the washing performance is reduced. In addition, the drum type has a much worse foam removal during rinsing than the pulsator type. For this reason, except for some brands, when washing with a drum-type washing machine using Japanese-made clothing detergent, foam overflows from the washing layer at the time of washing, and extremely remains after rinsing, The reality was that it could not withstand use.

Problems to be Solved by the Invention The present invention is to provide a cleaning composition having low foaming during cleaning and excellent rinsing properties.

Constitution of the Invention The cleaning composition of the present invention comprises the following (a), (b),
It is characterized by containing the three components (c) satisfying the following conditions (1) to (4).

(A), (b) the total amount of both components is (a) +
(B) = 1 to 15% by weight.

(A), (b) the blending weight ratio of both components is (a) /
(B) = 0.1-3.

(C) The compounding amount of the component is 0.05 to 0.5% by weight.

(A) A nonionic surfactant obtained by adding an average of 8 to 30 moles of an alkylene oxide to a primary or secondary alcohol having 8 to 18 carbon atoms.

(B) A fatty acid soap having 12 to 22 carbon atoms.

(C) No. 4 rotor with a B-8H type viscometer, a silicone compound comprising an organic silicone having a viscosity of at least 20 P at 25 ° C. at 20 rpm and hydrophobic fine particles.

As the nonionic surfactant of the component (a), the following (a-1) and (a-2) are representative.

(A-1) Either an average of 8 to 30 moles of a primary or secondary alcohol ethylene oxide (EO) having 8 to 18 carbon atoms added thereto
Nonionic surfactant.

(A-2) Primary or secondary alcohols having 8 to 18 carbon atoms
An EO-PO type nonionic surfactant to which EO is added in an average of 8 to 20 mol and propylene oxide (PO) is added in an average of 3 to 15 mol.

In the case of the EO-type nonionic surfactant, if the number of moles of EO added is less than 8, sufficient rinsing properties cannot be obtained.
If the amount is more than mol, the effect of improving the detergency is poor, and this is not preferred as a detergent component.

In the case of the EO-PO type nonionic surfactant, if the number of moles of EO added is less than 8, sufficient dispersion and solubility in water cannot be obtained, while if it exceeds 20 moles, the effect of improving the detergency is poor. If the number of moles of added PO is less than 3, the effect of improving rinsing properties is small, and if it exceeds 15 moles, sufficient dispersion and solubility in water cannot be obtained. In the EO-PO type nonionic surfactant, EO and PO may be added randomly or in blocks, and in the latter case, the order of addition is not limited.

The preferred EO addition mole number of the EO type nonionic surfactant is 15
EO-PO type, EO = 8 to 15, PO = 3
Those having an additional mole number of from 10 to 10 are preferred.

Among the nonionic surfactants (a), EO-
PO type nonionic surfactants are preferred.

The fatty acid soap of the component (b) has an average carbon number of 12 to
22 saturated or unsaturated fatty acid salts are used. As the salt, an alkali metal salt, particularly a sodium salt, is suitable.

In the composition of the present invention, the component (a) and the component (b)
The total content of the components is 1 to 15% by weight, preferably 5 to 10%.
% And the weight ratio (a) / (b) of both components is 0.1 to
3, preferably in the range of 0.1 to 2.

If the total amount of both components (a) and (b) is less than 1% by weight, a sufficient rinsability improvement effect cannot be obtained, while if it exceeds 15% by weight, high-hardness water (5 ° DH or more) is used. Detergency decreases.

On the other hand, if the mixing ratio (a) / (b) is out of the above range, a sufficient rinsing property improving effect cannot be obtained.

As the silicone compound (c), a mixture of an organic silicone such as dimethylpolysiloxane and a hydrophobic fine powder such as hydrophobic silica and a divalent metal salt of a fatty acid is used. Here, as the organic silicone, a No. 4 rotor having a viscosity at 25 ° C. by a B-8H type viscometer and having a viscosity of 20 P (poise) or more when measured at 20 rpm is used. If the viscosity is less than 20P, sufficient foam-suppressing properties are not exhibited. Further, the organic silicone and the hydrophobic fine particles have a weight ratio of 9/1 to 1
It is desirable to mix in the range of / 9, whereby a good foam suppressing effect can be obtained.

The organic silicone may be simply mixed and adsorbed to the hydrophobic fine particles, or may be bonded to the surface of the hydrophobic fine particles by a silane coupling reaction.

The silicone compound as the component (c) is incorporated in the detergent composition of the present invention in an amount of 0.05 to 0.5% by weight. If the amount is less than 0.05% by weight, no sufficient defoaming effect is exhibited.

Various optional components can be added to the detergent composition as needed. Optional components include anionic surfactants, other nonionic surfactants, surfactants such as cationic surfactants, zeolites, water-soluble phosphate-free calcium-trapping chelate builders, carbonates, alkali builders such as silicates, enzymes, A sodium percarbonate, a sodium perborate bleach, a reducing agent such as a sulfite, a re-contamination inhibitor such as carboxymethylsemelose and polyethylene glycol, an optical brightener, and bentonite may be used as required. it can.

Examples of the anionic surfactant include the following.

1) a linear alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms; 2) an α-olefin sulfonate having an average of 10 to 20 carbon atoms; 3) an alkyl sulfate having an average of 10 to 20 carbon atoms; An alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms and having an average of 0.5 to 8 moles of ethylene oxide added thereto; Sulfonate of fatty acid lower alkyl ester represented or disalt of fatty acid sulfonate (R: alkyl group or alkenyl group having 10 to 20 carbon atoms Y: alkyl group having 1 to 3 carbon atoms or counter ion Z: counter ion) The counter ion in these anionic surfactants is usually sodium or potassium. Alkali metal salts are suitable.

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) ... (I
I) (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, and generally x is from 0.7 to 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; polyacrylate; Hydroxy polyacrylate, polyitaconate, polyacetal carboxylate, salt of a copolymer of acrylic acid and maleic anhydride, salt of a copolymer of maleic anhydride and methyl vinyl ether, copolymer of maleic anhydride and olefin Polymer electrolytes such as a salt of a polymer and a salt of a copolymer of acrylic acid and methacrylic acid are exemplified.

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

As the enzyme, protease, lipase, cellulase, amylase, keratinase and the like can be added.

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
Preferably, the composition is 1.2 g / cc.For example, such a composition is kneaded with each detergent component as described in 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. Some or all of the detergent components can be supplied in the form of a spray-dried product and kneaded.

Effects of the Invention According to the detergent composition of the present invention, (a) a nonionic surfactant, (b) a fatty acid soap and (c) a silicone compound are blended, and the blending amount of each component is specified. ) And (b), by setting the total amount and ratio of the components within a predetermined range, not to mention a combination with a low-foaming surfactant, as well as a general-purpose high-foaming anionic surfactant or nonionic surfactant. Even when an activator is added, foaming during washing can be suppressed to a low level, and foaming can be quickly eliminated even during rinsing, and rinsing can be completed in a short time.

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.

(1) Preparation of a soil cloth A 10 wt% benzene solution of organic soil containing the following soil components is uniformly applied to a cotton skin shirt so that the weight of the fiber is 0.1 wt%, and air-dried to obtain a soil cloth. Prepared.

Soil component Soil composition (wt%) Oleic acid 40.6 Triolein 22.4 Cholesterol oleate 17.5 Liquid paraffin 3.6 Squalene 3.6 Cholesterol 2.3 Gelatin 10.0 (2) Method for evaluating foaming and rinsing properties V695 type drum washing machine manufactured by Bosch West Germany Using 3 と DH water, the organic dirt is applied under the following washing conditions: washing bath volume 15, rinsing bath volume 28, cloth to be washed 4 kg, detergent concentration 0.333%, temperature 25 ° C. Using a skin shirt as a cloth to be washed, program washing was performed.

The washing program used the standard course without prewashing.
In this program, after washing (about 30 minutes) → preliminary rinsing,
It is repeated three times of pool rinsing (about 10 minutes) and dehydration.

Under these conditions, the foaming at the end of the washing and the rinsing property at the end of the third pool rinsing were evaluated according to the following criteria.

Foaming 5: No foaming at all 4: Foam is 20mm or less, tapping and washing of the cloth to be washed is performed sufficiently 3: Foaming is 20 to 50mm, tapping and washing of the cloth to be washed is slightly weaker 2: Foaming stands at least 50mm The cloth to be washed only moves slowly in the foam.1: The foam fills the washing tub and the foam overflows from the detergent inlet.5: Rinsing property 5: Almost no foam is recognized 4: Foam of 5 mm or less Remains 3: Bubbles of 5 to 10 mm or less remain 2: Bubbles of 10 to 20 mm remain 1: Bubbles of 20 mm or more remain Examples Examples Nonionic surfactants and silicone compounds are obtained from the detergent composition shown in Table 1 below. And 45% solids using each component excluding a part of zeolite for grinding aid
Was prepared. This detergent slurry was dried at a hot air temperature of 380 ° C. using a countercurrent spray drying tower so that the water content was 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 Iron Works) 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 discharge port of the kneader, and the kneaded product was formed into a cylindrical pellet of about 5 mmφ × 10 mm.

Crusher (Speedmill ND-10 type Okada Seiko Co., Ltd.) with 2 times the weight (weight ratio) of cooling air at 15 ° C
Was introduced. At this time, at the same time, 4 parts by weight of zeolite having an average temporary particle size of 1 μm (water content: 15%) was added as a grinding aid to 100 parts by weight of the pellets.

The crusher has a 15 cm long cutter with four crosses, rotates at 3000 rpm, and the screen is made of 360-degree punched metal. This crusher is continuously connected in three stages,
Hole diameter of each screen is 1st stage; 3.5mm ^φ , 2nd stage: 2m
m ^φ , third stage; 1.5 mm ^φ . After separating the particles that have passed through the crusher in three stages from the cooling air, the fragrance is sprayed to obtain a bulk density of 0.
8 g / cc of washed particles were obtained.

By adding these silicone compounds and enzymes, the cleaning composition of the present invention having the composition shown in Table 1 was obtained,
Foaming and rinsing properties were evaluated.

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

AOS-K; C_14-18α-olefin sulfonate potassium α-SF-Na; C_12-18α-Sulfo fatty acid methyl ester
Thorium LAS-K; straight chain alkyl group having 10 to 14 carbon atoms in the alkyl group
Potassium benzenesulfonate LAS-Na; a linear alkyl group having 10 to 14 carbon atoms in the alkyl group
Sodium sensulfonate Nonionic surfactant A; C_12-13Primary alcohol or C
_12-14EO, PO adduct of secondary alcohol (EO, PO addition mole number
Is described in the section of properties of the nonionic surfactant A in the table) Nonionic surfactant B; C_12-13Primary alcohol EO = 2
0 mole adduct Soap; tallow soap sodium zeolite; A-type synthetic zeolite (average particle size 0.9 μm) Silicate-Na; Na_TwoO: SiO_Two= 1: 2.2 Carbonic acid-K; K_TwoCO_Three(Reagent product) Carbonic acid-Na; Na_TwoCO_Three(Reagent product) Sulfite-Na; Sodium sulfite (Reagent product) Silicone compound A: Dimethylpolysiloxane / phobic
Aqueous silica = 9/1 (weight ratio) reactive silicone compa
Und. No.4 in B-8H type viscometer [Tokyo Keiki Co., Ltd.]
Rotor, viscosity at 20 rpm = 50P (25 ° C) Silicone compound B: dimethylpolysiloxane / loose
Aqueous silica = 5/5 (weight ratio) non-reactive silicone resin
Pound. N in B-8H type viscometer [Tokyo Keiki Co., Ltd.]
o.4 rotor, viscosity at 20 rpm = 30P (25 ° C) Protease; Sabinase 4.0T (Novo) Lipase; Lipolase 100T (Novo)

Continuation of the front page (72) Inventor Tsuneharu Mukaiyama 1-3-7 Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (56) References JP-A-52-136894 (JP, A) JP-A-63-258998 (JP, A) (58) Fields surveyed (Int. Cl. ⁶ , DB name) C11D 10/04 C11D 3/37 C11D 1/72 WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A nonionic surfactant obtained by adding an average of 8 to 30 moles of an alkylene oxide to a primary or secondary alcohol having 8 to 18 carbon atoms, (b) a fatty acid soap having 12 to 22 carbon atoms and (c) A) No. 4 rotor with a B-8H type viscometer, a silicone compound composed of an organic silicone having a viscosity of 20P or more at 25 ° C. and a hydrophobic fine particle at 25 ° C. when measured at 20 rpm: 0.05
And the total blending amount of the component (a) and the component (b) is 1 to 0.5% by weight.
A detergent composition characterized by being in a range of 15% by weight and a blending amount of the component (a) and the component (b) in a weight ratio of (a) / (b) = 0.1-3. Stuff.