JP3398286B2 - Liquid detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent which has good storage stability, excellent detergency and is capable of imparting flexibility to clothing.

[0002]

2. Description of the Related Art Liquid detergents generally have better solubility in water than powder detergents and can be directly applied to a soiled portion, but liquid detergents can be stored more easily than powder detergents. It has difficult problems such as separation and precipitation, and in some cases transparency is required. Therefore, liquid detergents have many restrictions in their compounding conditions. For example, as a hardness-reducing component, zeolite that is generally used in powder detergents is water-insoluble, so that it is difficult to stably compound it into liquid detergents. Citric acid (salt) is commonly used as a hardness-reducing component in liquid detergents.
Although polycarboxylic acid type chelating agents such as the above are used, care should be taken when blending a large amount from the viewpoint of stability.

Other important builder components include carboxylic acid polymers. The carboxylic acid-based polymer has an excellent dispersibility for dispersing mud stains and the like in the washing liquid, and plays a role of preventing reattachment of loose stains to the fibers. Typical carboxylic acid-based polymers include homopolymers or copolymers of unsaturated carboxylic acids such as acrylic acid, maleic acid or fumaric acid, but it is more difficult to compound in a liquid detergent than polycarboxylic acids. However, since the polymer itself is difficult to dissolve in the liquid detergent, problems such as separation and turbidity are likely to occur, and it is extremely difficult to mix an effective amount.

On the other hand, there has been known a technique for improving the softness and texture of clothing by adding a cationic surfactant to a detergent composition. For example, Japanese Unexamined Patent Publication No. 59-15498 discloses a detergent composition containing a nonionic surfactant and a mono-long chain alkyl cationic surfactant, and Japanese Unexamined Patent Publication No. 59-25896 discloses a nonionic surfactant. A detergent composition containing an agent, an alkyl glucoside, and a dilong-chain quaternary ammonium salt is disclosed. However, since these cationic surfactants originally have a tendency to redeposit stains, there is a dilemma that the detergency is not sufficiently exerted while the softness and texture are improved. Although it was considered to use the above-mentioned carboxylic acid-based polymer in order to prevent redeposition, the carboxylic acid-based polymer is particularly unstable in the presence of a cationic surfactant, and precipitation, suspension, etc. Not only the stability but also the detergency and the softness cancel each other out, and it is almost impossible to formulate the composition to exert the effect of preventing redeposition.

Therefore, an object of the present invention is to provide a liquid detergent composition which is capable of providing a detergent having flexibility and can obtain a detergency superior to that of conventional detergents and, in addition, is excellent in stability after storage. Especially.

[0006]

Means for Solving the Problems As a result of various investigations, the present inventors have found that when a cationic surfactant capable of imparting flexibility to clothing is blended, a composition is obtained by blending a specific polymer compound. It was found that the effect of imparting flexibility and an excellent detergency can be obtained while maintaining the stability, and the present invention has been completed.

That is, the present invention comprises (A) 10 to 60% by weight of a surfactant other than the cationic surfactant, (B) 0.1 to 10% by weight of the cationic surfactant, and (C) a polyether compound. A liquid detergent composition containing 0.1 to 15% by weight of a polymer compound obtained by graft-polymerizing a monoethylenically unsaturated monomer mainly containing acrylic acid and / or methacrylic acid on a backbone chain Is.

Examples of the component (A) of the present invention include (a) a nonionic surfactant and (b) an anionic surfactant. As the nonionic surfactant as the component (a), the following (1) to
One or more selected from (3) can be used. (1) Having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol or an alkyl group or an alkenyl group derived from a branched alcohol having an average carbon number of 8 to 20, and having an average of 1 to 2
Polyoxyethylene alkyl or alkenyl ethers with 0 moles of ethylene oxide added. (2) A polyoxyalkylene alkyl or alkenyl ether having an alkyl group or an alkenyl group having an average carbon number of 8 to 20 to which an average of 1 to 15 mol of ethylene oxide and an average of 1 to 5 mol of propylene oxide are added. In this case, addition of ethylene oxide and propylene oxide may be random or block. (3) Alkyl polysaccharide surfactant R ⁵ — (OR ⁶ ) _x G _y (a) represented by the following general formula (a) [In the formula, R ⁵ is a linear or branched carbon number 8 to 18 Alkyl group, alkenyl group, or alkylphenyl group of R ⁶
Represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. These nonionic surfactants can be added to the composition in an amount of 10 to 60% by weight, preferably 15 to 50% by weight.

As the anionic surfactant as the component (b), one or more selected from the following (4) to (7) can be used. (4) An alkylbenzene sulfate having an alkyl group having an average carbon number of 10 to 20. (5) It has an alkyl group derived from a linear primary alcohol or a linear secondary alcohol or an alkyl group derived from a branched alcohol having an average carbon number of 10 to 20, and has an average of 0.5 to 6 in one molecule.
Alkyl ether sulfate added with moles of ethylene oxide. (6) An alkyl or alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20. (7) A fatty acid salt having an average carbon number of 8 to 20.

The counterion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and ethanolamine, and mixtures thereof. When the anionic surfactant is blended, it may be blended in the detergent composition in an acid form or may be neutralized with an alkali (ethanolamine or the like) added separately in the composition. These anionic surfactants can be incorporated in the composition in an amount of 0 to 30% by weight, preferably 2 to 20% by weight.

In the present invention, the weight ratio of the nonionic surfactant (a) to the anionic surfactant (b) is
(A) / (b) = 2/1 to 15/1 is preferable.

The cationic surfactant as the component (B) is represented by the following general formula (1)

[0013]

[Chemical 2]

[Wherein any one or two of R ¹ , R ² , R ³ and R ⁴ is an alkyl group or an alkenyl group having a carbon number of 12 to 20, and the rest are the same or different and have a carbon number of 1 to 1].
5 alkyl group, hydroxyalkyl group or formula- (C
H ₂ CH ₂ O) _m H (m is the average number of moles of ethylene oxide added and is a number of 2 to 20), and x is a halogen atom, CH ₃ SO ₄ or CH ₃ CH. ₂ SO
_{Shows 4} . ] The cationic surfactant represented by These cationic surfactants are present in the composition at 0.1
10 to 10% by weight is blended.

The polymer compound as the component (C) is a polymer compound obtained by graft-polymerizing a monoethylenically unsaturated monomer mainly containing acrylic acid and / or methacrylic acid onto the backbone of a polyether compound. As the polyether compound, the following general formula (2) Y—O (CH ₂ CH ₂ O) _n H (2) (wherein Y is hydrogen, methyl group, phenyl group or benzyl group, preferably methyl group or phenyl It is a group, and n is an average number of moles added, and a group represented by 2 to 200) is preferable.

The polymer compound (C) of the present invention is obtained by graft-polymerizing a polyether compound with acrylic acid or methacrylic acid as an essential component and other unsaturated carboxylic acid. Examples of unsaturated carboxylic acids that can be used in addition to acrylic acid and / or methacrylic acid include maleic acid, fumaric acid, itaconic acid and maleic anhydride. As the polymerization initiator, a known radical initiator can be used. The polymer compound (C)
Most obtained by reacting a polyether compound which is a main chain with a monoethylenically unsaturated monomer containing acrylic acid and / or methacrylic acid in a weight ratio of at least 1/4 or more. preferable. A specific method for producing a polymer compound is as follows:
By separately and slowly adding the monoethylenically unsaturated monomer and the initiator while stirring the polyether compound at a temperature of not less than 0 ° C, preferably 100 to 200 ° C.
An acid type polymer compound of the present invention can be obtained. When forming a salt, it can be easily obtained by neutralizing with an alkali agent such as sodium hydroxide after cooling, and like the anionic surfactant, it is added to the composition in the acid form as it is, It may be neutralized in. The polymer compound (C) is
0.1 to 15% by weight in the composition, preferably 0.5 to 1
0% by weight is compounded.

The weight ratio of the component (C) to the component (B) is preferably (C) / (B) = 1/10 to 10/1. Particularly preferably (C) / (B) = 1/2 to 2
At / 1, the liquid detergent composition of the present invention exhibits excellent stability.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Although the balance of the composition of the present invention is water, it is possible to add, as an optional component, components conventionally known to be incorporated in detergents. As such optional components, polymers such as polyethylene glycol and carboxymethyl cellulose; color transfer inhibitors such as polyvinylpyrrolidone; metal scavengers such as citric acid, diglycolic acid, phosphoric acid or salts thereof; alkali carbonates, alkali metal silicates Alternatively, alkaline agents such as alkanolamines (mono, di, triethanolamine) (which can also be used as pH adjusters); proteases, cellulases, lipases,
Enzymes such as amylase; enzyme stabilizers such as calcium chloride, formic acid, boric acid (boron compounds); antifoaming agents such as silicone / silica; lower alcohols such as ethanol; benzene sulfonate, p-toluene sulfonic acid, etc. Lower alkylbenzene sulfonates; propylene glycol,
Glycols such as polypropylene glycol, ethylene glycol, polyethylene glycol; benzoates (also effective as preservatives), solubilizers such as urea; butyl hydroxytoluene, distyrenated cresol, sodium sulfite, sodium bisulfite, etc. Inhibitors; other examples include fluorescent dyes, bluing agents, fragrances, antimicrobial preservatives, and the like.

[0019]

The present invention will be described in the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 <Synthesis of Polymer Compound (1)> In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 100 parts by weight of phenoxy polyethylene glycol having an average molecular weight of 1500 and malein. Charge 5 parts by weight of acid, heat under nitrogen stream to dissolve, and stir 15
The temperature was raised to 0 ° C. Next, while maintaining the temperature at 150 to 151 ° C., 30 parts by weight of acrylic acid and 4.5 parts by weight of di-t-butyl peroxide were separately added dropwise continuously over 1 hour, and then stirring was continued for 40 minutes. It was After cooling, 135 parts by weight of pure water was added to obtain a polymer compound (1).

Synthesis Example 2 <Synthesis of polymer compound (2)> In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 100 parts by weight of phenoxy polyethylene glycol having an average molecular weight of 2000 and malein. Charge 10 parts by weight of acid and heat to dissolve under a nitrogen stream.
The temperature was raised to 45 ° C. Next, while maintaining the temperature at 145 to 147 ° C., 50 parts by weight of acrylic acid and 2.5 parts by weight of di-t-butyl peroxide were continuously added dropwise over 1 hour, and then stirring was continued for 80 minutes. It was After cooling
150 parts by weight of pure water was added to obtain a polymer compound (2).

Synthesis Example 3 <Synthesis of polymer compound (3)> In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser, 100 parts by weight of monomethoxypolyethylene glycol having an average molecular weight of 1,500, 10 parts by weight of maleic acid was charged, heated under nitrogen stream to dissolve, and heated to 145 ° C. with stirring. Next, the temperature is 145 to 147 ° C.
15 parts by weight of acrylic acid and 1.0 part by weight of di-t-butyl peroxide were separately added dropwise continuously over 1 hour, and the stirring was continued for 100 minutes thereafter. After cooling, 125 parts by weight of pure water was added to obtain a polymer compound (3).

Synthesis Example 4 <Synthesis of polymer compound (4)> In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser, 100 parts by weight of monomethoxypolyethylene glycol having an average molecular weight of 2000, 10 parts by weight of maleic acid was charged, heated under nitrogen stream to dissolve, and heated to 145 ° C. with stirring. Next, the temperature is 145 to 147 ° C.
While maintaining at 50 parts by weight, 50 parts by weight of acrylic acid and 2.5 parts by weight of di-t-butyl peroxide were separately added dropwise continuously over 1 hour, and then stirring was continued for 60 minutes. After cooling, 150 parts by weight of pure water was added to obtain a polymer compound (4).

Example 1 Various detergent compositions were prepared using the polymer compounds (1) to (4) obtained in the above synthesis example and the components shown in Table 1, and the storage stability and mud reconstitution were performed by the following methods. The anti-adhesion performance was measured.
The results are shown in Table 1.

1) Storage stability test Each composition was placed in a 100 ml glass bottle and sealed. This sample was stored in a constant temperature bath at 50 ° C. and 5 ° C. for 10 days. The sample after storage was visually judged by the following criteria. : No separation, precipitation or cloudiness △: Slightly cloudy ×: Separation, precipitation or cloudiness 2) Mud redeposition prevention performance test method A white cotton cloth (gold cloth 2003 cloth) was cut into 10 cm x 10 cm There were 5 sheets as one set. Kanuma red clay for horticulture was added to 1 liter of an aqueous detergent solution for evaluation, and a test was conducted under the following conditions with a tergotometer. <Experimental conditions> Washing time 10 minutes Detergent concentration 0.08% Water hardness 4 ° Water temperature 20 ° C Rinse 20 ° C Rinse with tap water for 5 minutes Re-contamination prevention ability is the original cloth (white cloth) before cleaning and The reflectance of the contaminated cloth after the test at 460 nm was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the redeposition prevention rate was calculated by the following formula. Redeposition prevention rate (%) = (reflectance after test / reflectance of original fabric) × 100

[0026]

[Table 1]

Nonionic surfactant (1): Emulgen 120 (Kao Corporation) Nonionic surfactant (2): Softanol 70 (Nippon Catalyst Co., Ltd.) Nonionic surfactant (3): Nonidet R -9 (Shell Japan Co., Ltd.)-Nonionic surfactant (4): polyoxyethylene alkyl ether / alkyl glucoside having 12 carbon atoms, 8 moles of average EO addition and 2 moles of average PO addition: general formula (a) In, R ⁵ = alkyl group having 8 to 16 carbon atoms, x = 0, y = 1.3, G =
Glucose residue-LAS-Na: sodium linear alkylbenzene sulfate having 10 to 14 carbon atoms-ES-Na: sodium polyoxyethylene alkyl ether sulfate (average carbon number 10 to 12, average EO addition mole number 2.5) -fatty acid : Lunack L-55 (Kao Corporation) -Cationic surfactant: Kotamine 86W (Kao Corporation) -Durazyme 16.0L: Protease (Novo Nordisk BioIndustry Co., Ltd.)-Lipolase 100L: Lipase (Novo Nordisk Bio) Industry Co., Ltd.)-Chino Pearl CBS-X: fluorescent dye manufactured by Ciba-Geigy Co., Ltd.-Balance: Amount to make the whole 100

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C11D 10/02 C11D 10/02 // (C11D 10/02 1:68 1:68 1:72 1:72 1: 722 1: 722 1:22 1:22 1:14 1:14 1:16 1:16 1:12 1:12 1:04 1:04 1:62 1:62 3:37 3:37 1:40 1:40) (72) Inventor Masaki Tsumadori 1334 Kao Co., Ltd. Minato, Wakayama City, Wakayama Prefecture (72) Inventor Takuya Saeki 1 992, Okihama, Nishihama, Aboshi Ward, Himeji City, Hyogo Prefecture (72) Inventor Masato Takagi 1 992 Nishioki Okihama, Aboshi-ku, Himeji-shi, Hyogo Pref., Polymer Research Laboratory, Nippon Shokubai Co., Ltd. (56) Reference JP 63-260994 (JP, A) JP 8-208770 (JP, A) Special Kaihei 8-208769 (JP, A) JP 54-142209 (JP, A) JP 63-291999 (JP, A) JP 7-53993 (JP A) (58) investigated the field (Int.Cl. ^7, DB name) C11D 1/00 C11D 3/00 C11D 10/00 C08L 51/00

Claims (5)

(57) [Claims] 1. A surfactant other than (A) a cationic surfactant in an amount of 10 to 60% by weight, and (B) a cationic surfactant of 0.
1 to 10% by weight and (C) a monoethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid in the backbone of the polyether compound represented by the following general formula (2) (A) nonionic surfactant and (b) anionic surfactant as (A), containing (a) / (b) = 2/1
A liquid detergent composition containing a weight ratio of ˜15 / 1. Y—O (CH ₂ CH ₂ O) _n H (2) (wherein Y is a phenyl group, n is the average number of moles added, and 2
The number is ~ 200. ) 2. The (B) cationic surfactant has 12 carbon atoms.
The liquid detergent composition according to claim 1, which is an amine salt or an ammonium salt of mono-long-chain alkyl or di-long-chain alkyl of 20 to 20. 3. The cationic surfactant (B) is represented by the following general formula (1): [In the formula, any one or two of R ¹ , R ² , R ³ , and R ⁴ is an alkyl group having 12 to 20 carbon atoms or an alkenyl group, and the rest are the same or different and are alkyl groups having 1 to 5 carbon atoms. ,
Hydroxyalkyl group or the formula _{- (CH 2 CH 2 O)} m H
(M is the average number of moles of ethylene oxide added, 2 to
It is the number of 20. ) Represents a group represented by, x is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO _4. ] The liquid detergent composition of Claim 1 or 2 which is a cationic surfactant represented by these. 4. The liquid cleaning according to claim 1, wherein the ratio of the component (C) to the component (B) is 1/10 to 10/1 in terms of the weight ratio of (C) / (B). Agent composition. 5. The (C) polymer compound is a trunk chain polyether compound, and the weight ratio of the monoethylenically unsaturated monomer containing acrylic acid and methacrylic acid is at least ¼ or more. The liquid detergent composition according to any one of claims 1 to 5 , which is obtained by reacting at a ratio of.