JP3264837B2 - Concentrated 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 concentrated liquid detergent composition containing a surfactant at a high concentration and exhibiting stable and excellent washing performance.

[0002]

BACKGROUND OF THE INVENTION Liquid detergents generally have the advantage of being more soluble in water than powder detergents and have the advantage that they can be directly applied to contaminated parts.
It has advantages such as not requiring complicated equipment such as drying equipment. However, there is a problem of stability such as phase separation, precipitation or turbidity not found in powder detergents, and it is necessary to nervously consider combinations of surfactants, types of alkaline agents, water content, and the like. In particular, not only water-insoluble substances such as zeolites, but also other metal ion sequestering agents, and the incorporation of builder substances such as dispersants such as polymers cause stability to be impaired. Have attention. Usually, in order to improve stability, it has been proposed to mix a solvent such as ethylene glycol, propylene glycol or ethanol with a hydrotrope such as p-toluenesulfonate, but compared to powder detergents, It is difficult to incorporate an appropriate amount of builder.

On the other hand, in recent liquid detergents, attempts have been made to increase the concentration of surfactants and reduce the amount of water in the system, thereby reducing the standard usage amount and making the detergent compact. However, such a concentrated liquid detergent makes the formulation of the liquid detergent itself more nervous than ever, and even more, it is more difficult to incorporate a large amount of a builder.

[0004] Japanese Patent Application Laid-Open No. 7-53993 describes a solid particle which can be stably blended in a liquid detergent, particularly a builder excellent in mud stain cleaning power and anti-redeposition property. The builder described in the above publication is a polymer compound in which (meth) acrylic acid and a monoethylenically unsaturated monomer are grafted onto a polyethylene glycol as a backbone, and a nonionic surfactant is used at a high concentration. For example, there is no description about builder performance or detergency in a system in which a nonionic surfactant accounts for 80% by weight or more of the surfactant. Nonionic surfactants are excellent in cleaning properties against oil stains, and compared to anionic surfactants,
Since the critical micelle concentration is low, it is advantageous for downsizing. However, development of a more stable builder, which is easily affected by the composition of the builder, has been desired.

[0005] Accordingly, an object of the present invention is to provide a concentrated liquid detergent containing a nonionic surfactant as a main surfactant without deteriorating the stability and the mud stain cleaning performance and re-adhesion prevention performance. An object of the present invention is to provide an excellent liquid detergent composition.

[0006]

As a result of various studies, the present inventors have found that by blending a specific polymer compound in a system containing a high concentration of a surfactant containing a nonionic surfactant, it is possible to obtain a stable polymer. The inventors have found that they have excellent detergency without impairing the properties, and have completed the present invention.

That is, the present invention relates to a concentrated liquid detergent composition having a water content of not more than 60% by weight, wherein (A) a surfactant having a proportion of nonionic surfactant of not less than 80% by weight is 20%. 0.1 to 15% by weight of a polymer compound obtained by graft polymerizing a monoethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid to the backbone of the polyether compound (B). The present invention provides a concentrated liquid detergent composition containing 1% by weight. Hereinafter, the concentrated liquid detergent composition of the present invention will be described in detail.

As the nonionic surfactant of the component (A) of the present invention, it is particularly preferable to use a polyethylene oxide and / or polypropylene oxide type nonionic surfactant, and in particular, the following (1) to (3) It is preferable to mainly use one or more selected from the group consisting of

(1) A polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 mol of ethylene oxide to a primary alcohol having 8 to 16 carbon atoms. (2) An average of ethylene oxide is added to a secondary alcohol having 8 to 16 carbon atoms. 5 to 15 mol of polyoxyethylene alkyl ether added (3) An average of 5 to 15 mol of ethylene oxide and an average of 1 to 5 mol of propylene oxide were added to a primary or secondary alcohol having 8 to 16 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether. The order of addition of ethylene oxide and propylene oxide is not particularly limited, and may be block polymerization or random polymerization. Which substance is used depends on the use, purpose and stability of the cleaning agent.

Other nonionic surfactants include polyoxyethylene alkyl phenyl ethers, sucrose fatty acid esters, fatty acid glycerin monoesters, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides, amine oxides and the like. Alkyl glycosides are exemplified, and as the alkyl glycoside, alkyl glycosides represented by the following general formula (a) are preferable. _{^{R 1 - (OR 2) x}} G y (a) wherein, R ¹ is straight or branched chain alkyl group having 8 to 18 carbon atoms, an alkenyl group, or alkylphenyl group, R ²
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. The stability of the liquid detergent composition is further improved by adding 1 to 10% by weight, preferably 1 to 5% by weight of the alkyl glucoside in the composition.

In the present invention, the nonionic surfactant accounts for at least 80% by weight of the total surfactant, which is suitable not only for detergency and stability but also for compactness. Since the concentrated liquid detergent composition of the present invention has a high surfactant concentration, the viscosity tends to be high. In this case, in order to reduce the viscosity of the liquid detergent, the nonionic surfactants (1) to (3) are preferably used in combination with those derived from primary alcohols and those derived from secondary alcohols.

[0012] The concentrated liquid detergent composition of the present invention contains 15% by weight or less in a surfactant in addition to the nonionic surfactant.
Preferably, 1 to 10% by weight of an anionic surfactant can be blended. As the anionic surfactant, a surfactant which is usually compounded in a detergent can be used. In particular, a sulfonate type, a sulfate type and / or a carboxylate type anionic surfactant is preferably used. You. Specifically, those shown in the following (4) to (7) are most preferable. (4) An alkylbenzene sulfate having an alkyl group having an average of 10 to 20 carbon atoms. (5) having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 10 to 20 or an alkyl group derived from a branched alcohol, and having an average of 0.5 to 6 in one molecule;
Alkyl ether sulfate to which moles of ethylene oxide have been added. (6) An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms. (7) Fatty acid salts having an average carbon number of 8 to 18.

The counter ion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and ethanolamines and mixtures thereof. When the above-mentioned anionic surfactant is blended, a method of blending in an acid form and adding an alkali (ethanolamine or the like) separately may be used.

As other surfactants, cationic surfactants and zwitterionic surfactants which are known to be added to detergents may be added as long as the stability is not impaired.

[0015] The concentrated surfactant composition of the present invention has a high total surfactant concentration of 20 to 80%, preferably 30 to 60% by weight.

The polymer compound (B) is a polymer compound obtained by graft-polymerizing a monoethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid onto the backbone of a polyether compound. As the polyether compound, the following general formula (1) YO (CH ₂ CH ₂ O) _n H (1) (where Y is hydrogen, methyl, phenyl or benzyl, preferably methyl or phenyl) And n is an average number of moles added, preferably 2 to 200). In particular, those having a polyethylene glycol skeleton and one end having an alkyl group or an aryl group such as a phenyl group or a benzyl group are preferable. In the concentrated liquid detergent composition of the present invention, those having a methyl group or a phenyl group in the main chain can be most stably compounded.

Unsaturated carboxylic acids that can be used other than acrylic acid and / or methacrylic acid include maleic acid,
Fumaric acid, itaconic acid, maleic anhydride and the like. The high molecular weight water-soluble polymer of the present invention is obtained by adding an unsaturated carboxylic acid to a polymer essentially containing acrylic acid and methacrylic acid and graft-polymerizing the polyether compound. Known radical initiators can be used as the polymerization initiator. A polymer compound is obtained by reacting a monoethylenically unsaturated monomer containing acrylic acid and methacrylic acid at a weight ratio of at least 1/4 or more with a polyether compound as a main chain. Are most preferred. As a specific method for producing a polymer compound, a monoethylenically unsaturated monomer and an initiator are separately separated while stirring a polyether compound at 90 ° C. or higher, preferably 100 to 200 ° C. under a nitrogen stream. ,
The acid compound of the present invention can be obtained by dropping slowly and slowly. In the case of forming a salt, it can be easily obtained by cooling and neutralizing with an alkali agent such as sodium hydroxide. As in the case of the anionic surfactant, it may be compounded in an acid form and neutralized in a liquid detergent. The polymer compound is incorporated in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight.

The polymer compound of the present invention comprises a monoethylenically unsaturated monomer containing acrylic acid and methacrylic acid in a weight ratio of at least 1/4 or more based on the polyether compound as the main chain. It is obtained by reacting.

The balance of the composition of the present invention is water. The water content of the concentrated liquid detergent of the present invention is 60% by weight or less, particularly 40% by weight.
Even in the case where the content is less than the weight%, a stable liquid detergent can be obtained.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The concentrated liquid detergent composition of the present invention can contain, as an optional component, a component which has been conventionally known to be added to a detergent, as long as stability and detergency are not spoiled. . For example, polymers such as polyethylene glycol and carboxymethyl cellulose; anti-transfer agents such as polyvinylpyrrolidone; metal scavengers such as citric acid, diglycolic acid, phosphoric acid or salts thereof; alkali carbonates, alkali metal silicates or alkanolamines Alkaline agent (can also be used as a pH regulator); Enzymes such as protease, cellulase and lipase; Enzyme stabilizers such as calcium chloride, formic acid and boric acid; Antifoaming agents such as silicone; Lower alcohols such as ethanol; Lower alkylbenzene sulfonates such as sulfonic acid salts and p-toluenesulfonic acid; glycols such as propylene glycol, ethylene glycol, polypropylene glycol and polyethylene glycol; solubilisers such as benzoate and urea; The Styrene cresol, sodium sulfite, antioxidants such as sodium bisulfite; Tinopal CBS (manufactured by Ciba-Geigy)
And the like, a bluing agent, a generally known fragrance which is generally stable in a liquid detergent, an antibacterial preservative and the like.
Among these optional components, propylene glycol or ethylene glycol exhibits the property of further improving the stability of the concentrated liquid detergent, but a large amount is meaningless and disadvantageous for downsizing. It is preferably at most 20% by weight and at most 15% by weight.

[0021]

EXAMPLES The present invention will be described below with reference to 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, 5 parts by weight of an acid were charged and dissolved by heating under a stream of nitrogen, and stirred for 15 minutes.
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 dropped continuously over 1 hour, and thereafter, stirring was continued for 40 minutes. 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 2,000, 10 parts by weight of an acid are charged and dissolved by heating under a stream of nitrogen, and
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 separately dropped continuously over one hour, and thereafter, stirring was continued for 80 minutes. 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 inlet tube, and a reflux condenser, 100 parts by weight of monomethoxy polyethylene glycol having an average molecular weight of 1500, 10 parts by weight of maleic acid was charged, dissolved by heating under a nitrogen stream, and heated to 145 ° C. with stirring. Next, the temperature was set to 145 to 147 ° C.
, 15 parts by weight of acrylic acid and 1.0 part by weight of di-t-butyl peroxide were separately dropped continuously over 1 hour, and thereafter, stirring was continued for 100 minutes. 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 inlet tube, and a reflux condenser, 100 parts by weight of monomethoxy polyethylene glycol having an average molecular weight of 2,000 was added. 10 parts by weight of maleic acid was charged, dissolved by heating under a nitrogen stream, and heated to 145 ° C. with stirring. Next, the temperature was set to 145 to 147 ° C.
, 50 parts by weight of acrylic acid and 2.5 parts by weight of di-t-butyl peroxide were separately dropped 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 examples and the components shown in Tables 1 and 2,
The storage stability and the mud re-adhesion prevention performance were measured by the following methods. The results are shown in Tables 1 and 2.

1) Storage stability test Each composition was placed in a 100 ml glass bottle and sealed. This sample was stored in a thermostat at 50 ° C. and 5 ° C. for 10 days. The sample after completion of storage was visually judged according to the following criteria. : No separation, sedimentation or cloudiness Δ: Slightly cloudy ×: Separation, sedimentation or cloudiness occurred 2) Test method for preventing mud reattachment White cotton cloth (2003 cloth) was cut into 10 cm x 10 cm. And a set of five sheets. Gardening Kanuma Red Clay was added to 1 liter of the detergent aqueous solution for evaluation, and a test was performed with a tergotometer under the following conditions. <Experimental conditions> Washing time 10 minutes Detergent concentration 0.08% Water hardness 4 ° Water temperature 20 ° C Rinsing Rinse with 20 ° C tap water for 5 minutes The re-contamination prevention ability is the original cloth (white cloth) before cleaning and The reflectance at 460 nm of the contaminated cloth after the test was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the re-contamination prevention rate was determined by the following equation. Recontamination prevention rate (%) = (Reflectance after test / Reflectance of original cloth) × 100

[0028]

[Table 1]

[0029]

[Table 2]

Nonionic surfactant (1): Emulgen 120 (Kao Corporation) Nonionic surfactant (2): Softanol 70 (Nippon Shokubai Co., Ltd.) Nonionic surfactant (3): Nonidet R -9 (Shell Japan Co., Ltd.)-Nonionic surfactant (4): polyoxyethylene alkyl ether having 12 carbon atoms, 8 average EO addition moles, and 2 average PO addition moles-alkyl glucoside: general formula (a) R ¹ = alkyl group having 8 to 16 carbon atoms, x = 0, y = 1.3, G =
Glucose residue ・ LAS-Na: sodium 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 : Lunac 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.) ・ Chinopearl CBS-X: fluorescent dye manufactured by Ciba-Geigy Japan Co., Ltd. ・ Balance: quantity to make the whole 100

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C11D 1: 722) C11D 1: 722) (72) Inventor Masaki 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Takuya Saeki Nippon Shokubai Polymer Research Institute, Inc., 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji, Hyogo (72) Inventor Masato Takagi 992, Nishioki, Okihama-ji, Abashiri-ku, Himeji-shi, Hyogo Nippon Shokubai Polymer Research Institute, Inc. (56) References JP-A-8-208769 (JP, A) JP-A-7-53993 (JP, A) JP-A-3-177406 (JP, A) JP-A-63-260994 (JP, A) JP-A-2 -127500 (JP, A) Table 10 -502694 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-19/00

Claims (4)

(57) [Claims] 1. A concentrated liquid detergent composition having a water content of 60% by weight or less, wherein (A) a surfactant having a proportion of a nonionic surfactant of 80% by weight or more is 20 to 80% by weight. wt%, for the trunk chain of the polyether compound, the mono-ethylenically unsaturated monomer mainly composed of acrylic acid and / or methacrylic acid (B) represented by the following general formula (1)
A concentrated liquid detergent composition containing 0.1 to 15% by weight of a polymer compound obtained by graft polymerization at a ratio of at least 1/4 or more . Y—O (CH ₂ CH ₂ O) _n H (1) (where Y is a methyl group, a phenyl group or a benzyl group, and n is
It is an average number of moles added, and is a number of 2 to 200. ) 2. A polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 mol of ethylene oxide to a primary or secondary alcohol having 8 to 16 carbon atoms, or a non-ionic surfactant having 8 to 16 carbon atoms. An average of 5 to 1 ethylene oxide is added to primary alcohol or secondary alcohol.
The concentrated liquid detergent composition according to claim 1, wherein the composition is at least one selected from polyoxyethylene polyoxypropylene alkyl ethers to which 5 mol and propylene oxide are added in an average of 1 to 5 mol. 3. The concentrated liquid detergent composition according to claim 1, wherein the content of the anionic surfactant is 15% by weight or less. 4. A surfactant containing 30 to 80% by weight.
The concentrated liquid detergent composition according to claim 1.
object.