JP2002327199A - Liquid detergent composition for clothes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition which is used for clothes, has a good washing performance, holds a stable quality, even when stored for a long period, has a proper viscosity, when used, and scarcely changes the viscosity, when the temperature is changed. SOLUTION: This liquid detergent composition for clothes comprises (a) 10 to 30 wt.% of a nonionic surfactant represented by general formula (1): R-O-(EO)n H (1) [R is a 10 to 20C alkyl or alkenyl; EO is oxyethylene; (n) is an integer of 8 to 26], (b) 0.05 to 1.0 wt.% of a protease enzyme, (c) an antibacterial solvent, and (d) a cross-link type carboxyvinyl polymer, and has a liquid viscosity of 50 to 1,000 mPa.s at a liquid temperature of 10 to 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition for clothing. More specifically, the present invention relates to a liquid detergent composition for clothing comprising a nonionic surfactant, a protease enzyme, an antimicrobial solvent, and a cross-linked carboxyvinyl polymer.

[0002]

2. Description of the Related Art In the field of liquid detergent compositions, many studies have been made to improve the washing performance without separating components in the composition, that is, while maintaining the appearance stability. For example, Japanese Patent Application Laid-Open No. 9-87664 discloses a composition containing a specific fatty acid monoethanolamide as a main component and having excellent viscosity, foaming properties, detergency, and low-temperature stability. Japanese Patent Application Laid-Open No. H11-241094 discloses a system in which a nonionic surfactant and an anionic surfactant are blended, a specific nonionic surfactant is used, and the ratio of a cationic substance to an anionic surfactant is further increased. A liquid detergent composition having excellent cleaning performance and excellent storage stability is disclosed by limiting the following. Further, Japanese Patent Application Laid-Open
Japanese Patent No. 293289 discloses liquid washing for clothing that uses a sodium soap of a higher unsaturated fatty acid, glycols and an alkaline electrolyte to greatly improve detergency, and is also excellent in low-temperature stability and prevention of recontamination by scum. An agent is disclosed.

On the other hand, in addition to the above-mentioned cleaning ability and appearance stability, researches relating to liquid viscosity are also being vigorously conducted.
For example, Japanese Patent Application Laid-Open No. 1-215897 discloses a composition having a pH of 11 to 13 and a viscosity determined by a Haake Rotobisc viscometer as a composition useful for various cleaning purposes. This composition contains a crosslinked polycarboxy polymer as a thickener and is gelled. JP-A-2-123193 discloses an alkylglycoside and a water-soluble polymer, in which irritation and damage to the skin are alleviated, foaming power is excellent, and rinsing after washing is excellent. A cleaning composition suitable for cleaning hard surfaces such as tableware is disclosed. In addition, Japanese Patent Laid-Open No.
The publication discloses a transparent gel detergent containing an anionic surfactant, a polyhydric alcohol and a carboxyvinyl polymer. Further, JP-A-6-159089 discloses that
Disclosed is a liquid detergent composition containing a thickener and a fatty acid or a salt thereof in addition to N-acylglutamate, and having a pH of 6.0 or less. Since this composition has an appropriate viscosity due to the above composition, it is a liquid detergent composition that is easy to handle, excellent in usability, and high in safety.

As described above, in order to adjust the liquid viscosity, a thickener or a fatty acid salt is usually used, and sometimes it is used in combination. Generally, a thickener is often added to a cleansing agent for the skin or the like because of the necessity of increasing the degree of gelation. On the other hand, in the liquid detergent composition for clothing, since various components are blended for the purpose of improving the detergency, there is a problem in that the appearance stability is reduced by simply adding a thickener. In addition, enzymes, in particular, protease enzymes are added to the current detergent composition for clothing in order to improve the detergency of sebum stains. However, when a polymer that generally serves as a thickener is blended, the polymer has a strong property of capturing calcium,
As a result, calcium, which is a stabilizer of the enzyme, is affected, so that the enzyme tends to be deactivated over time. Therefore, fatty acid salts are often used to adjust the viscosity.

[0005] However, the fatty acid salt has a problem that the viscosity greatly increases and decreases due to a change in temperature, and in particular, the viscosity becomes high at a low temperature, which hinders the use, that is, the usability deteriorates. Liquid washing for clothing which has such excellent washing performance, satisfies the quality such as liquid stability and antibacterial property, has a suitable viscosity at the time of use, and has a small fluctuation of the liquid viscosity with temperature changes. Agents are needed.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid detergent for clothing which has good washing performance especially for sebum stains, maintains a stable quality even during long-term storage, and is suitable for use. It is an object of the present invention to provide a liquid detergent composition for clothing having a suitable viscosity and having a small change in viscosity with respect to a temperature change.

[0007]

The inventors of the present invention have conducted intensive studies and have found that, in addition to a specific nonionic surfactant, a protease enzyme, and an antibacterial solvent, a crosslinked carboxyvinyl polymer is used as a thickener. A novel liquid cleaning composition having high cleaning ability, excellent long-term stability, and suitable viscosity and its stability was developed by the addition of, and the present invention was completed.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Accordingly, the present invention provides a liquid composition comprising (a) a nonionic surfactant, (b) a protease enzyme, (c) an antibacterial solvent, and (d) a crosslinked carboxyvinyl polymer. The present invention relates to a liquid detergent composition for clothing having a viscosity.

The present invention further provides the above component (a),
A method for producing a cleaning composition according to the invention comprising mixing (b), (c) and (d), and a method for cleaning clothing using the cleaning composition according to the invention. Also concerns. The invention also relates to the use of the cleaning composition according to the invention in the cleaning of clothing. Here, clothing includes clothing or clothing or materials thereof, for example, fabrics, as well as cloth or yarn products not intended to be worn, and a cleaning composition for clothing refers to washing of clothing. Refers to a composition intended to do so.

The (a) nonionic surfactant used in the present invention may be any type of nonionic surfactant as long as a desired effect can be obtained. Alkenyl ether type nonionic surfactants are preferred. Preferably, the nonionic surfactant used in the present invention has a general formula (1): R—O— (EO) n—H (1) (where EO represents an oxyethylene group (—CH ₂ CH ₂ O— )
).

In the general formula (1), R is an alkyl group or an alkenyl group, and preferably has 10 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. An alkyl group having 12 to 15 carbon atoms is particularly preferred from the viewpoint of detergency. The alkyl group or alkenyl group may be linear or branched, but it is preferable to use a primary nonionic surfactant. This is because secondary nonionic surfactants tend to have lower detergency than primary nonionic surfactants.

In the general formula (1), n represents the average number of moles of ethylene oxide (EO) added. The average number of moles of ethylene oxide added is not particularly limited as long as the desired effect can be obtained, but is preferably in the range of 8 to 26 from the viewpoint of sebum stain detergency. The average number of moles added is more preferably 9 to 25, particularly preferably 12 to 20, and most preferably 15 to 20.

The amount of the nonionic surfactant in the composition according to the present invention may be any ratio as long as the required detergency and viscosity can be obtained.
From the viewpoints of low foamability and economy, 10% of the present liquid detergent composition is used.
To 30% by mass, more preferably 1 to 30% by mass.
It is in the range of 5 to 25% by mass. If the amount of the nonionic surfactant component is too small, for example, if it is less than 10% by mass, the detergency tends to be inferior. If it is too large, for example, 30% by mass.
When the amount exceeds the above range, a gelling region peculiar to the nonionic surfactant is entered, and a sharp increase in viscosity occurs, so that viscosity control tends to be difficult. The nonionic surfactants may be used alone or in combination of two or more.

When the above nonionic surfactant is used in combination with another nonionic surfactant, the nonionic surfactant to be used is not particularly limited, but is preferably 10% in view of the viscosity and appearance stability of the composition. Or less, more preferably 5% or less. Anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, olefin sulfonates, alkyl ether sulfates, and fatty acid salts can also be used in combination, but the viscosity and appearance stability of the composition can be reduced. To 1% or less.

[0015] The protease enzyme (b) contained in the composition according to the present invention has an action of decomposing dirt to make it easy to remove, and is particularly useful for sebum dirt. Therefore,
As the protease enzyme, any type of protease can be used as long as it has such an action. As an example, Savinase16L (no
vozimes), Everlase16L (nov
ozymes), Purafect L (GENEN)
COR), Properase L (GENENCO)
R company).

The amount of the protease enzyme in the composition of the present invention is not particularly limited, and may be an amount usually used in a liquid detergent composition. 0.05 to in the liquid detergent composition
The content is preferably 1.0% by mass, more preferably 0.1 to 0.5% by mass. The effect of the protease enzyme is even more pronounced when the composition according to the invention is applied to specific parts of clothing. The protease enzymes may be used alone or in combination of two or more.

The antibacterial solvent contained in the composition according to the present invention is formulated from the viewpoint of maintaining low preservative power and from the viewpoint of low-temperature stability. Solvents effective for both antiseptic and low-temperature stability include ethanol, phenoxyethanol, polyalkylene glycol monophenyl ether, polyalkylene glycol monoalkyl ether, and the like. The amount of these antibacterial solvents is not limited as long as the desired effect can be obtained, but is preferably 4 to 20% by mass, more preferably 7 to 15% by mass. Because the antibacterial solvent
Even if it is too large, for example, if it is blended in excess of 20% by mass,
This is because the antibacterial performance tends to plateau. The antibacterial solvents may be used alone or in combination of two or more.
For stabilization at low temperatures, it is preferable to use a glycol-based solvent such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol as an auxiliary agent.

In order to improve the detergency, the composition according to the present invention may be blended with an alkaline agent such as an alkanolamine. Alkanolamines that can be incorporated into the composition according to the present invention include, for example, alkanolamines represented by the following formula: (HO—R ₃ ) _p —NH _(3-p) (wherein, R ₃ represents an alkylene group, and p represents an integer of 1 to _3. ) In the above formula, R ₃ is preferably Carbon number 1
5, more preferably an alkylene group having 1 to 3 carbon atoms can be suitably used. The alkylene group may be linear or branched. Specifically, preferred alkylene groups include, for example, a methylene group, an ethylene group, and a propylene group. Specific examples of alkanolamines, preferably, monoethanolamine,
Diethanolamine, triethanolamine and the like.
The compounding amount of the alkanolamine is usually 0.5 to 15% by mass, preferably 1 to 7% by mass. Generally, within this range, an effect of improving detergency against oily stains and protein stains can be obtained.

In order to improve the detergency of proteins and the like other than sebum stains, enzymes such as lipase, amylase and cellulase may be added, and the ratio is preferably 0 to 1% by mass.
Furthermore, 0 to 4% by mass of silicone such as dimethyl silicone, polyether-modified silicone and amino-modified silicone is used to improve the texture, and 0.00001 to 0.001% by mass of a dye such as an acid dye is used for coloring the liquid detergent composition. In addition, a fragrance can be incorporated in an amount of 0.1 to 0.5% by mass for aroma.

A list of perfume raw materials that can be used as perfumes is found in various literatures, such as "Perfume and Flavor C"
chemicals ", Vol. Iand II, Steffen Arctander, Allured
Pub.Co. (1994) and "Synthetic Fragrance Science and Product Knowledge",
Motoichi Indo, Chemical Daily, 1996 and Perfume an
d Flavor Materials of Natural Origin '', SteffenArc
tander, Allured Pub. Co. (1994) and "Encyclopedia of Fragrance", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Flower
oils and Floral Compounds In Perfumery '', Danute L
ajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

Typical fragrances include aliphatic hydrocarbons,
Hydrocarbons such as terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, ethers such as aliphatic ethers and aromatic ethers, aliphatic oxides, terpene oxides and the like Oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes and aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzene Aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols,
Phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones,
Lactones such as terpene lactones, hydrogenated aromatic lactones, aromatic lactones, aliphatic esters, furan carboxylic esters, aliphatic cyclic carboxylic esters, cyclohexyl carboxylic esters, terpene carboxylic esters, aromatic Esters such as carboxylic acid esters, nitro musks, nitriles, amines, pyridines,
It is possible to use a mixture of one or more of synthetic fragrances such as quinolines, pyrroles, indole and other nitrogen-containing compounds and natural fragrances from animals and plants, and compounded fragrances containing natural fragrances and / or synthetic fragrances. it can.

Specific fragrances include, for example, aldehydes C6 to C12, anisaldehyde, acetal R, acetophenone, acetylsedren, adoxal, allyl amyl glycolate, allyl cyclohexane propionate, alpha damascon, beta damascon, Delta damascon, ambrette lid, ambroxane,
Amylcinamic aldehyde, amylcinamic aldehyde dimethyl acetal, amyl valerianate,
Amyl salicylate, isoamyl acetate, isoamyl salicylate, aurantiol, acetyl-jugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, p-tert-butyl cyclohexanol, p-tert-butyl Cyclohexyl acetate, ortho tertiary butyl cyclohexanol, benzaldehyde, benzyl formate, caryophyllene, kashmelan, carvone, sedroambar, cerdyl acetate, cedrol, celestrid, cinnamic alcohol, cinnamaldehyde, cis jasmon, citral, citral dimethyl Acetal, Citrasar, Citronellal, Citronello Le, citronellyl acetate, citronellyl formate, citronellyl nitrile, Shikurasetto, cyclamen aldehyde, Shikurapuroppu, Caron, coumarin, cinnamyl acetate, delta C6~
C13 lactone, dimethylbenzylcarbinol, dihydrojasmon, dihydrolinalool, dihydromyrcenol, dimetol, dimyrcetol, diphenyloxide, ethylvanillin, jugenol, fluitate,
Fentyl alcohol, phenylethylphenyl acetate, garaki solid, gamma-C6-13 lactone, α-pinene, β-pinene, limonene, myrcene, β
-Caryophyllene, geraniol, geranyl acetate, geranyl formate, geranyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-
3-hexenyl salicylate, hexyl cinamic aldehyde, hexyl salicylate, hyacinth dimethyl acetal, hydrotropic alcohol, hydroxycitronellal, indole, ionone, isobornyl acetate, isocyclocitral, iso-E super, isoyugenol, isononyl acetate , Isobutylquinoline, jasmar, jasmolactone, jasmofilan, koabon, rigstral, lilial,
Lime oxide, linalool, linalool oxide, linalyl acetate, liral, manzanate, mayol, menthanyl acetate, menthsonate, methyl anthranilate, methyl jugenol, menthol, alpha methyl ionone, beta methyl ionone,
Gamma methyl ionone, methyl isoeugenol, methyl lavender ketone, methyl salicylate, muge aldehyde, mugol, musk TM-II, musk 781, musk C14, muscone, cibetone, cyclopentadecanone, cyclohexadecenone, cyclopentadecanol Do
Ambrettolide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide,
12-oxahexadecanolide, ethylene brassate,
Ethylene dodecandioate, oxahexadecene-2
-One, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musk tibetin, nopyr alcohol, nopyr acetate, neryl acetate, nerol, methyl phenyl acetate, mirac aldehyde, neobergamate, oakmoss No,
1. Oribbon, Oxyphenylone, Paracresil Methyl Ether, Pentalid, Phenylethyl Alcohol, Phenylethyl Acetate, Alpha Pinene, Lubafuran, Rosephenone, Rose Oxide, Sandaroa, Sandella, Santa Rex, Styril Real Acetate, Styril Real Propionate, terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydrolinalyl acetate, tetrahydrogeraniol, tetrahydrogeranyl acetate, tonalid, traseolide, tripral, thymol, wanilin, verdox, yayala, anise oil, bay oil,
Boad rose oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil , Geranium oil, hiba oil, cypress oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, patchouli oil, peppermint oil, perilla oil, petitgren oil, Pine oil, rose oil, rosemary oil, camphor oil, fragrance oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, crocodile bean tincture, vetiver Oil, ylang-ylang oil, grapefruit oil, yu Oil, benzoin, Peru balsam, tolu balsam, tuberose oil, Musukuchinki,
Castorium tincture, civet tincture, ambergris tincture. In addition, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene, or the like can be used as a solvent or a retaining agent for the fragrance.
In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example.

In order to obtain a suitable viscosity, the composition according to the present invention further comprises (d) a crosslinked carboxyvinyl polymer as a thickener. The crosslinked carboxyvinyl polymer contained in the composition according to the present invention is a water-soluble or water-dispersible vinyl polymer having a carboxyl group, and mainly refers to a copolymer in which acrylic acid is copolymerized with allyl sucrose or the like. Preferred crosslinked carboxyvinyl polymers for use in the compositions according to the present invention are those copolymerized with a multivinyl or multiallyl functional crosslinker. The crosslinked carboxyvinyl polymer is preferably copolymerized with a polyalkenyl polyether of a polyhydric alcohol. The polyhydric alcohol used for this preferably has at least 4 carbon atoms and 3 hydroxy groups. Examples of these are described in US Pat.
And U.S. Pat. No. 4,130,501.
Preferred crosslinked carboxyvinyl polymers are formed from α-β monoolefinically unsaturated lower aliphatic carboxylic acids crosslinked with a polyol polyether. The polyol is preferably an oligosaccharide, a reduced derivative of an oligosaccharide in which the carbonyl group has been converted to an alcohol group, or pentaerythritol. Preferably, the polyol has its hydroxy group etherified with an allyl group and has at least two allyl groups per molecule of polyol. Suitable crosslinked carboxyvinyl polymers are formed from acrylic acid having a low polyallyl sucrose content.

The average molecular weight of the crosslinked carboxyvinyl polymer is preferably 500,000 or more, more preferably 1,000,000 or more. Specifically, as the crosslinked carboxyvinyl polymer, Carbopol 934, 940, 9
Preferred are 41, 675, 690, 980 and the like, and particularly preferred is Carbopol 940. The viscosity of the liquid detergent for clothing according to the present invention can be adjusted to 50 to 50 ° C. in a temperature range of 10 to 30 ° C. so that it can be applied locally to a target portion of clothing, for example, from the viewpoint of usability, that is, ease of use. ~ 1,000mP
a · s, more preferably 50 to 900 mPa · s, and particularly preferably 100 to 900 mPa · s.
８００800 mPa · s. If the viscosity is too low,
For example, when the viscosity is less than 50 mPa · s, when the cleaning agent is directly applied to the soil, the usability tends to be poor, such as difficulty in aiming and adjusting the amount. On the other hand, when the viscosity is high, for example, 1,000 mPa · s. On the other hand, if the viscosity is too high, it tends to be difficult to take out of the bottle and to remain on the cap or the like, which tends to be inconvenient.

Which viscosity is selected within the above range depends on
Consumer preferences are heavily involved, and consumer preferences are
It depends on age group, living area, and age. Accordingly, it is inefficient to develop the composition each time, and in order to set the composition within this range even when the temperature is different, it is necessary to make the composition less temperature-dependent. As a method for solving these problems, after setting a basic composition excellent in detergency, liquidity, antibacterial property, etc. by a cleaning component, a specific thickener is blended in an amount according to consumer's preference etc. The purpose is to establish a composition that maintains good quality within the leverage viscosity range.

Specifically, (a) a nonionic surfactant,
A suitable method is to mix a predetermined amount of (b) a protease enzyme and (c) an antibacterial solvent, and mix (d) a crosslinked carboxyvinyl polymer as a further component. As described above, in order to obtain a suitable viscosity of the detergent composition, the amount of the crosslinked carboxyvinyl polymer is preferably 0.01 to 0.5% by mass based on the mass of the detergent composition. More preferably, the cross-linked carboxyvinyl polymer is 0.03 to 0.3% by mass, particularly preferably 0.1 to 0.3% by mass.
It is from 0.5 to 0.2% by mass. If the amount is too small, for example, if it is less than 0.01% by mass, it is difficult to obtain a viscosity of 50 mPa · s. Conversely, if it is too large, if it exceeds 0.5% by mass, for example, a sharp increase in viscosity will occur. This is because the viscosity as a liquid detergent tends to be too high.

In general, when the viscosity is adjusted by a combination of surfactants or the viscosity is adjusted by adding a large amount of a thickener, the viscosity changes as the temperature of the liquid changes. It tends to be less convenient. However, when the crosslinked carboxyvinyl polymer in the above range is used, the fluctuation of the liquid viscosity is small even if the temperature of the liquid detergent changes, and the above-mentioned usability is inferior at a temperature of 10 to 30 ° C. which is used everyday. Absent.

The cleaning composition according to the present invention may be used in combination with other thickeners as long as the desired effects can be obtained, and it is possible to thicken even non-crosslinked polymers. However, these non-crosslinked polymers have poor thickening efficiency and require a large amount. In such a case, liquid separation or the like is likely to occur regardless of whether it is a synthetic polymer or a natural polymer, that is, the appearance stability is easily deteriorated, and the stability of the enzyme is adversely affected. Further, since the degree of spinnability, which is one of the physical properties of the liquid, increases, the liquid drainage property deteriorates, causing a problem in usability. Furthermore, since these thickeners hardly contribute to detergency, there is also a problem in terms of economy. In this regard, the crosslinked carboxyvinyl polymer used in the present invention does not have these disadvantages, and is a cleaning composition excellent in appearance stability, usability, and economy.

[0029]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. In this embodiment,
The garment detergent compositions of Examples 1 to 6 (Table 2) and Comparative Examples 1 to 6 (Table 3), which are the compositions according to the present invention, were prepared, and these were detergency, viscosity (30 ° C.) and viscosity ( 10 ° C.), appearance stability and antibacterial properties. The specific evaluation method is as follows.

(Evaluation Method) Evaluation method of detergency 1-1. Preparation of Artificial Soil Cloth Clay mainly composed of crystalline minerals such as kaolinite and vermiculite was dried at 200 ° C. for 30 hours and used as inorganic stain. After 3.5 g of gelatin was dissolved in 950 g of water at about 40 ° C., 0.25 g of carbon black was dispersed in water using a powerful emulsifying and dispersing machine, Polytron (manufactured by KINEMATICA, Switzerland). Next, 14.9 g of inorganic soil was added and emulsified with Polytron,
Further, 31.35 g of organic soil was added and emulsified and dispersed with Polytron to prepare a stable soil bath. 10cm in this dirty bath
× 20cm predetermined cleaning cloth (Cotton cloth 6 specified by the Japan Oil Chemical Association)
No. 0) is immersed, and water is squeezed with two rubber rolls.
The amount of stain was made uniform. Put this dirty cloth at 105 ° C for 3
After drying for 0 minutes, both sides of the soiled cloth were rubbed left and right twice. This is cut into 5 cm x 5 cm and the reflectance is 42.
Those having a range of ± 2% were applied to a dirty cloth.

The soil composition of the artificial soil cloth thus obtained is shown in Table 1.

[0032]

[Table 1]

1-2. Cleaning method Terg-O-Tometer (US Testin)
g), and put 10 artificially soiled cloths and a cotton knitted cloth into them, adjust the bath ratio to 30 times, 120 rpm, tap water (25 ° C., 4 ° DH) 900 ml, liquid detergent composition Was washed for 10 minutes under the condition of a concentration of 1000 ppm, rinsed with tap water (25 ° C., 4 ° DH) for 3 minutes, and finally dried using an iron. 1-3. Evaluation method The cleaning rate was determined by the Kubelka-Munk equation represented by the following equation 1. <Equation 1> Cleaning rate (%) = (K / S of contaminated cloth−K / S of cleaning cloth) /
(K / S of contaminated cloth−K / S of standard white cloth) × 100 K / S = (1−R / 100) ² / (2R / 100) where R is a color difference meter Σ-9000 made by Nippon Denshoku. Is the reflectance measured using As the standard white cloth, a clean cloth (cotton cloth No. 60 designated by the Japan Oil Chemical Association) was used. The evaluation of the cleaning rate was performed based on the average value of 10 test cloths, and the following criteria were used. Evaluation of cleaning rate: ：: cleaning rate of 70% or more ：: cleaning rate of 60% or more and less than 70% Δ: cleaning rate of 50% or more and less than 60% ×: cleaning rate of less than 50% Evaluation method of viscosity The liquid detergent composition was placed in a 300 ml tall beaker and placed in a 20 ml.
0 ml was taken and adjusted using a thermostatic water bath until the temperature of the liquid reached 10 ° C. or 30 ° C. Thereafter, a BL type viscometer (BROOK FIELD ENGINEERING L)
ABORATORIES, INC), rotor no.
The measurement was carried out at 30 rpm by using No. 2. 3. Evaluation method of appearance stability 150 ml of the liquid detergent composition was measured for a diameter of 50 mm and a height of 1
It was placed in a 00 mm cylindrical glass bottle, closed, and sealed.
In this state, after storage in a thermostat at 5 ° C. for one month, the appearance of the liquid was visually observed. The appearance stability was evaluated according to the following criteria. 3. Evaluation of appearance stability: ○: uniform △: slight precipitation or separation ×: large amount of precipitation or phase separation Evaluation method of antibacterial property The antibacterial property was evaluated using environmentally-derived gram-negative bacteria (rods), yeast, and mold as test bacteria. Bacteria were grown on Soybean Casein Digest Agar
The yeast was cultured for 4 hours on a potato dextrose agar medium for 48 hours, and the mold was cultured on a potato dextrose agar medium for 7 days.

Bacteria and yeast are suspended in sterile physiological saline at a concentration of about 1 × 10 ⁶ to 1 × 10 ⁷ cells / mL, and mold is suspended in physiological saline containing 0.005% dioctyldodecyl sodium sulfosuccinate. × 10 ⁶ cells / mL were suspended to give a test bacterial solution. After adding 0.2 mL of the test bacterial solution to 20 g of the evaluation sample and mixing well,
C., yeast and mold were stored at 25.degree. After 28 days, 1 g of each sample was aseptically collected, diluted and mixed with 9 mL of Soybean Digest Lecithin Polysorbate 80 liquid medium. Take 1 mL of the mixture in a Petri dish, and place the bacteria on Soybean Casein Digest Lecithin Polysorbate 80 Agar Medium, yeast and mold on glucose, peptone,
Pouring was performed on lecithin polysorbate 80 agar medium. Bacteria were cultured at 30 ° C. for 4 days, and yeast and mold were cultured at 25 ° C. for 7 days, and the number of surviving bacteria in the sample was measured.

In each case, the measurement was evaluated as pass if the number decreased to 0.01% or less with respect to the number of inoculated bacteria after 28 days, and rejected if not reached. <Test Bacteria (Test Bacterial Solution Concentration)> Gram-negative bacteria: Sta. Genus HE (1.3 × 10 ⁷ /
mL) Yeast: Fungus for yeast (4.5 × 10 ⁶ / mL) Mold: Black koji mold Aspergillus nigger
(1.1 × 10 ⁶ cells / mL) Evaluation of antibacterial activity: A: All 3 cells passed B: 2 cells passed, 1 cell failed C: 2 cells or more failed

[0036]

[Table 2]

[0037]

[Table 3]

[0038] The mass% in Tables 2 and 3 is the mass% of the indicated raw material relative to the entire detergent composition. The details of the raw materials used in the table are as follows. (A) Nonionic surfactant Doba25EO9: Branched chain containing 1 having 12 to 15 carbon atoms
Prepared by adding an average of 9 moles of ethylene oxide to a secondary alcohol (Dovanol 25) (AE25-9A, manufactured by Mitsubishi Chemical Corporation) Doba25EO15: Ethylene oxide is added to a branched chain primary alcohol having 12 to 15 carbon atoms (Dovanol 25). Prepared by adding an average of 15 mol (AE25-15A, manufactured by Mitsubishi Chemical Corporation) Doba25EO20: Prepared by adding an average of 20 mol of ethylene oxide to a branched chain primary alcohol having 12 to 15 carbon atoms (Dovanol 25) (Mitsubishi Chemical Dia13EO5: a branched-chain primary alcohol ethoxylate having 13 carbon atoms (average number of moles of ethylene oxide added: 5, prepared by adding ethylene oxide to Diadol 13 (Mitsubishi Chemical) using KOH as a catalyst. Lion) Chemical Co., Ltd.) Dia13EO15 : A branched chain primary alcohol ethoxylate having 13 carbon atoms (average number of moles of ethylene oxide added: 15, diadol 13 (Mitsubishi Chemical) to KOH
Prepared by adding ethylene oxide using as a catalyst. Dia13EO30: Branched primary alcohol ethoxylate having 13 carbon atoms (average number of moles of ethylene oxide added: 30; Diadol 13 (Mitsubishi Chemical) with KOH
Prepared by adding ethylene oxide using as a catalyst. Secondary alcohol EO9: prepared by adding an average of 9 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (Leocoal SC-90, manufactured by Lion Chemical Co., Ltd.) (b) Protease enzyme Savinase 16L: Novozymes Evarlase 16L: Novozymes (c) Antibacterial solvent Ethanol: 95% methanol-denatured ethanol TAMB: Trialkylene glycol monobutyl ether (Leosolve 703B, Lion Chemical Co., Ltd.) MEMP: Phenoxyethanol (Phenyl glycol PhG, Nippon Emulsifier Co., Ltd.) DEMB: diethylene glycol mono-butyl ether (butyl diglycol (95), manufactured by Nippon emulsifier Co., Ltd.) (d) a thickening agent Carbopol 940: cross-linked polyamide Acrylic acid (Carb
opol 940, B.I. F. Goodrich) Polyacrylic acid: polyacrylic acid, mass average molecular weight 60
00, pure content 40% (Polyty A-530, manufactured by Lion Chemical Co., Ltd.) Xanthan gum: Xanthan gum (KELZAN T,
CP Kelco) alkanolamine DEA: diethanolamine (Diethanolamine)
ine, manufactured by Union Carbide) Other components PEG: polyethylene glycol, weight average molecular weight 10
00 (PEG # 1000, manufactured by NOF Corporation) Dye: Yellow No. 203 (Quinoline Yellow WG-G)
CONC, manufactured by Chuo Gosei Chemical Co., Ltd.) Fragrance composition:

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

[Table 9]

[0045]

[Table 10]

[0046]

[Table 11]

[0047]

[Table 12]

[0048] The mass% in Table 4 is the mass% based on the fragrance composition.

[0049]

INDUSTRIAL APPLICABILITY The liquid detergent composition for clothing according to the present invention is excellent in cleaning performance against sebum dirt, has stable quality without causing problems such as liquid separation and microbial contamination, and is suitable in a normal use temperature range. Liquid viscosity, and there is little change in liquid viscosity even when the temperature changes.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C11D 3/37 C11D 3/37 3/386 3/386 3/48 3/48 F term (reference) 4H003 AC08 AC09 BA12 DA01 EB04 EB06 EB14 EB30 EB36 EB41 EC02 FA04 FA06 FA16 FA26 FA30 FA34 4H011 AA02 BA01 BA06 BB03 BC04 BC06 BC19 BC21 DA12

Claims (1)

[Claims] 1. (a) 10 to 30% by mass of a general formula (1): R—O— (EO) n—H (1) (wherein R is an alkyl or alkenyl group having 10 to 20 carbon atoms) EO is an oxyethylene group, n is an average number of moles added and is a numerical value in the range of 8 to 26), and (b) 0.05 to 1.0
(C) an antibacterial solvent;
(D) a cross-linked carboxyvinyl polymer, wherein the liquid viscosity at a liquid temperature of 10 to 30 ° C is 50 to
A liquid detergent composition for clothing having 1,000 mPa · s.