JPH1192788A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liq. detergent compsn. which is excellent in capability for cleaning natural fiber products and gives clothes a good feel to the touch by compounding an unsatd. carboxylic acid oligomer having a specified structure. a nonionic surfactant, and another surfactant. SOLUTION: 0.1-10 wt.%, pref. 0.1-5 wt.%, unsatd. carboxylic acid oligomer having an average mol.wt. of 500-50,000, pref. 1,000-10,000, and obtd. by the copolymn. of maleic acid, a 1-8C olefin, and another copolymerizable monomer [e.g. (meth)acrylic acid, itaconic acid, or methacrylsulfonic acid], 0.5-10 wt.% nonionic surfactant of the formula: R<1> CONH(R<2> O)m (R<3> O)n H (wherein R<1> is a linear or branched 4-20C alkyl or alkenyl; R<2> and R<3> are each 2-4C alkylene; and m and n are each 0-5 provided 1<=m+n<=7, pref. 1<=m+n<=5), and 5-70 wt.%, pref. 10-60 wt.%. other surfactant are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a natural fiber typified by wool and the like, a chemical fiber typified by polyester and the like,
Or various fiber products consisting of these blended fibers,
For example, the present invention relates to a liquid detergent composition characterized by being able to wash well on a sweater or fashionable clothes, impart good touch to clothing, and have good storage stability.

[0002]

2. Description of the Related Art Natural fiber products such as wool generally have a dry mark, and washing at home is a specialized cleaning shop due to the difficulty in system and finishing. Often use. However, some of the dry mark garments can be washed with water-based detergents using a neutral detergent, and the development of a detergent with an excellent finish that does not damage fibers has made it possible to wash at home without hesitation. In addition, the development of textile processing technology has improved the durability during washing, and has led to the launch of a washing machine with a washing mode for dry mark clothing. It's even easier.

[0003] As a condition for washing these dry mark garments in a water system, it is preferable to wash them by hand or by applying a weak mechanical force in order to maintain the texture without damaging the fibers. However, clothing such as wool is not sufficiently wetted by water-based washing liquid and has poor permeability to the interior of textiles and the like, so that the washing property is insufficient, and improvement of this point is strongly demanded. .

As light detergents such as those for dry mark clothing, polyoxyethylene alkyl ethers, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates and the like are widely used as main cleaning bases. ing. In addition, there is little skin irritation,
Attention has been paid to a technique in which an alkyl glucoside or an amine oxide is blended because it has an excellent hand feel during use (Japanese Patent Publication No. 5-75799, Japanese Unexamined Patent Publication No. 4-11698).
JP-A-3-188195, JP-A-57-96096, JP-A
57-105496, JP-A-57-205499, JP-A-62-215699
JP-A-1-247496, JP-A-6-271457, JP-A-5-247492). In particular, by mixing ether-type nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl sulfate, alkyl glucoside and amine oxide, those suitable for the performance of the intended use have been found. I have.

[0005] Further, in a system containing a cationic surfactant for imparting flexibility, stability at a low temperature becomes a problem, and precipitation or crystallization occurs at a low temperature, and there is a drawback that it does not return to its original state. Japanese Patent Publication No. 61-2113 discloses that low-temperature stability and flexibility can be improved by including a specific anionic component and a cationic component in a specific ratio and adding a specific nonionic component in a predetermined ratio. Is described. Japanese Patent Application Laid-Open No. 4-153300 discloses that a nonionic surfactant-based cationic surfactant having a specific iodine value and a water-soluble silicone are blended to impart flexibility and to give a finished texture. It is stated that it will be better.

However, in these methods, stability and detergency are sacrificed in order to increase flexibility, and texture is sacrificed in order to maintain stability. In particular, in a system containing a cationic surfactant, a decrease in stability and detergency cannot be avoided by increasing the blending amount. In addition, a base such as silicone cannot impart a sufficient texture to natural fibers such as wool or blended fiber products thereof. Further, it is very difficult to add a polymer in terms of stability in order to improve detergency. Therefore, as a light detergent, research on a system which satisfies all of detergency, texture and stability has not been sufficiently conducted yet.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when a specific unsaturated carboxylic acid-based oligomer and a specific non-ionic surfactant are blended, especially wool or the like is obtained. The present inventors have found a stable liquid detergent composition which can perform a good washing of natural fiber products and give a good texture to clothing, and have completed the present invention.

That is, according to the present invention, (a) an average molecular weight of 500
Unsaturated carboxylic acid oligomer having a molecular weight of 0.1 to 10
(B) 0.5 to 10% by weight of a nonionic surfactant represented by the following general formula (I) and (c) a surfactant other than (b) 5
The present invention provides a liquid detergent composition containing about 70% by weight. <(B): Nonionic surfactant (I)> R ¹ CON (R ² O) _m H (R ³ O) _n H (I) (wherein, R ¹ is a straight or branched chain carbon number of 4 represents an alkyl group or alkenyl group of ~20, R ^2, R ³ is 2 carbon atoms
4 to 4 alkylene groups. m and n have a value of 0 to 5, 1
≦ m + n ≦ 7, preferably 1 ≦ m + n ≦ 5, the number of moles of alkylene oxide added. ).

In the present invention, the unsaturated carboxylic acid oligomer of the component (a) is incorporated in the composition in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight. (a) The amount of components is 0.
If it is less than 1% by weight, a sufficient cleaning effect cannot be obtained. When the content is 10% by weight or more, the stability of the composition is deteriorated.

In general, unsaturated carboxylic acid oligomers have an action of dispersing solid particle stains from clothes into a washing bath and an action of preventing the particles from reattaching (recontamination) to clothes, and are incorporated in the present invention. The detergency is further improved by blending an oligomer having a specific molecular weight as a component that can be used. In the present invention, the unsaturated carboxylic acid oligomer of the component (a) has an average molecular weight of 500 to 50,000, preferably
An unsaturated carboxylic acid type oligomer (hereinafter simply referred to as "oligomer"), which may be in the form of 1000 to 10,000 and partially in a salt form;
Maleic acid and olefins having 1 to 8 carbon atoms, acrylic acid,
Salts of copolymerized oligomers with copolymerizable monomers such as methacrylic acid, itaconic acid and methacrylic sulfonic acid, and / or salts of single oligomers such as acrylic acid, methacrylic acid and maleic acid. In particular, when the oligomer represented by the following formula (II) or / and the oligomer represented by the following formula (III) is used in combination with the cleaning composition of the present invention, it shows excellent performance. Was found.

[0011]

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Wherein Z is an olefin having 1 to 8 carbon atoms,
Maleic acid such as acrylic acid, methacrylic acid, itaconic acid and methacrylsulfonic acid, or a salt of a copolymer of maleic anhydride and a monomer copolymerizable with maleic acid, and m is a copolymer having a molecular weight of 500 to It is a value indicating 50000. M is _{Na, K, NH 4, H} . )

[0013]

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(Wherein P is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. L is a value such that the molecular weight of the homopolymer is 500 to 50,000. The homopolymer is a salt of Na, K and NH _4. ) The amount of the oligomer of the formula (II) and / or the oligomer of the formula (III) is based on 100 parts by weight of the surfactant (b) in the detergent composition. , 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Among these oligomers, polyacrylates (Na,
K and NH ₄ ) are particularly excellent. The average molecular weight of the oligomer is
500 to 30000, especially 1000 to 10000 are suitable. When the average molecular weight exceeds 30,000, the liquid stability decreases. If it is less than 500, no sufficient improvement in the effect can be seen.

In the present invention, the average molecular weight of the oligomer (a) is based on polyethylene glycol as standard,
The molecular weight distribution is obtained by measuring the solution fractionated by C using the light scattering intensity and the refractive index difference, and then calculating as the weight average molecular weight.

In the present invention, the nonionic surfactant (I) as the component (b) is used in an amount of 0.5 to 10% by weight, preferably 0.5 to 5% by weight.
By blending in weight%, the touch of clothing made of natural fibers represented by wool or the like can be improved in each step. (b) If the amount of the component is less than 0.5% by weight, the feel of clothing becomes insufficient. Further, even if it is blended in an amount of 10% by weight or more, almost no improvement in texture is observed. In formula (I), when R ¹ is an alkyl group or an alkenyl group, the preferred number of carbon atoms is 6-20.

The composition of the present invention contains a surfactant (c) other than the above (b). As the surfactant (c), (A)
A nonionic surfactant, (B) an anionic surfactant,
Any one or more of (C) a cationic surfactant and (D) an amphoteric surfactant can be used. Surfactant
(c) is 5 to 70% by weight in the liquid detergent composition of the present invention,
Preferably, the content is 10 to 60% by weight. However, the weight of the (B) anionic surfactant in the acid form is used.

Hereinafter, the specific surfactant (c) will be described. As the nonionic surfactant (A), conventional nonionic surfactants other than the component (b) can be blended.
Something like (3) can be used. (1) having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 8 to 20 or an alkyl group or an alkenyl group derived from a branched alcohol, and having an average of 1 to 20 moles of ethylene oxide; Added polyoxyethylene alkyl or alkenyl ether. (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 ethylene oxide has an average of 1 to 15 mol and propylene oxide has an average of 1 to 5 mol. In this case, ethylene oxide and propylene oxide may be either random addition or block addition. (3) An alkyl polysaccharide surfactant represented by the following general formula (i). R ^31- (OR ³² ) _x G _y (i) wherein R ³¹ is a linear or branched alkyl, alkenyl, or alkylphenyl group having 8 to 18 carbon atoms, and R ³² has 2 to 2 carbon atoms. An alkylene group of 4, 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. ].

As the (B) anionic surfactant, the following (4) to (7) can be used. (4) An alkylbenzene sulfonate 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 mol of ethylene oxide added per molecule; Alkyl ether sulfate. (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 20.

The counter ion of these anionic surfactants can be selected from cations such as sodium, potassium, magnesium and calcium and alkanolamines or mixtures thereof, but from the viewpoint of the stability of the composition. Particularly preferred are alkanolamines such as monomethyldiethanolamine or dimethylmonoethanolamine. When blending an anionic surfactant,
It may be incorporated into the detergent composition in the form of an acid, or may be neutralized with an alkali agent (alkanolamine or the like) added separately in the composition.

As (C) a cationic surfactant or (D) an amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid detergent composition of the present invention contains the above components (a), (b) and (c) and is suitable as a liquid detergent using water as a main medium. . Water is 30 ~
90% by weight, preferably 40-80% by weight. Within this range, the liquid detergent composition of the present invention is a stable composition.

In addition to the above-mentioned components (a), (b), (c) and water, components which are conventionally known to be added to detergents can be added as optional components. Such optional components include anti-staining agents 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 metal carbonates Alkaline agents such as alkali metal silicates or alkanolamines (which can also be used as pH regulators); enzymes such as proteases, cellulases, amylases and lipases; enzyme stabilizers such as calcium chloride, formic acid and boric acid; silicones Defoaming, fiber treatment or softening agent; lower alcohols such as ethanol; lower alkylbenzene sulfonates such as benzenesulfonate and p-toluenesulfonic acid; polyols such as propylene glycol, polypropylene glycol and glycerin; benzoates , Urea, etc. Solubilizers; butylhydroxytoluene, distyrenated cresol, antioxidants such as sulfites; other fluorescent dye, tinting agents, perfumes, and antimicrobials.

The concentration of the detergent composition of the present invention at the time of washing with a washing machine is preferably 0.067 to 0.167% by weight, and particularly, the concentration of the surfactant in the washing liquid is 0.02 to 0.16%.
Preferably, it is added so as to be 0.06% by weight. In addition, normal washing may be performed after hand washing and soaking for a while, and the detergent concentration in that case may be higher than that in normal washing, and specifically, 1.5 to 1.5 times in normal washing.
The concentration may be tripled.

Further, the liquid detergent composition of the present invention is intended for clothing which is vulnerable to alkalis or acids such as wool, and is therefore preferably a neutral liquid detergent composition having a pH of 6 to 8.

[0026]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A liquid detergent shown in Table 1 was prepared. The pH of the liquid detergent was adjusted to 7.0 using sodium hydroxide and hydrochloric acid.
The following evaluation was performed using the obtained liquid detergent. Table 1 shows the results.

(1) Evaluation of Detergency The detergency of the liquid detergent composition shown in Table 1 was evaluated by the following method. [Preparation of artificially contaminated cloth] Using the following AE dirt components,
An artificial soil solution was prepared. (Soil component) The amount of component B was adjusted so that the total of components A, B, C, D, and E became 100%. In addition, each% is a ratio in the final dirt component. A component: 0.44% lauric acid, 3.15% myristic acid, 2.35% pentadecanoic acid, 6.31% palmitic acid, 0.44% heptadecanoic acid, 1.60% stearic acid, 7.91% oleic acid
13.33% triolein, n-hexadecyl palmitate
A mixture of 2.22% and squalene 6.66%. B component: Calculate and weigh 105mg of calcium chloride (dihydrate).
Hard water obtained as 1000 ml by dissolving in distilled water C component: egg white lecithin liquid crystal 1.98% [arginine hydrochloride 11.37 g, histidine 4.20 g, serine 2.
After dissolving 44 g and adjusting the pH to 5.0 with concentrated hydrochloric acid, this solution and egg white lecithin were sufficiently mixed with a mixer to obtain an egg white lecithin liquid crystal. D component: Kanuma red clay 8.11% [Kanuma red clay was dried at 105 ° C for 5 hours, pulverized with an attritor, and the product passed through 150 mesh was used as mud. E component: carbon black 0.025% (Preparation of artificial soil liquid) Mix all A components, mix at 80 ° C while heating until a uniform solution is obtained, and then heat C component to 70 ° C. While stirring, the mixture was dissolved by stirring, and the component E was further added, and the mixture was stirred and uniformly dispersed. Further, the B component and the D component heated to 70 ° C. are added, and the mixture is sufficiently mixed at 70 ° C. using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., model M2-2.5). Liquid. (Preparation of Artificially Contaminated Cloth) A gravure type contaminating machine disclosed in JP-A-7-270395 was used for adhering the artificially soiled liquid to the cloth. The preparation conditions were as follows: gravure roll cell capacity: 58 cm ³ / m ² , coating speed: 1.0 m / min, drying temperature: 100 ° C., drying time: 1 minute. The cloth used was a wool muslin cloth. [Cleaning conditions and evaluation method] Five artificially contaminated cloths of 5 cm x 5 cm were put in 1 liter of a detergent aqueous solution for evaluation, and washed with a tergotometer at 50 rpm under the following conditions. (Washing conditions) Washing time 10 minutes Detergent concentration 0.133 wt% Water hardness 4 ° DH Water temperature 20 ° C. Rinse for 5 minutes in tap water * Detergency is 550 nm for the original cloth before and after cleaning.
Colorimeter (Nippon Denshoku Co., Ltd. Model)
Z-300A) and the cleaning rate (%) was determined by the following equation. Table 1 shows the measured average values of the five samples.

[0029]

(Equation 1)

(2) Evaluation of texture Processing method Fully automatic washing machine (manufactured by Matsushita Electric Industrial Co., Ltd .; NA-F60)
(K2 type), one commercially available sweater was put in, and washed in a hand washing course. The detergent concentration was 0.133% by weight, and water having a water temperature of 20 ° C. and a hardness of 4 ° DH was used. After washing,
Drying was performed by flat drying. The above process was repeated five times. Evaluation method The sweater treated by the above method was left in a constant temperature and humidity room at 20 ° C. and 65% Rh for 24 hours. About these sweaters,
Sensory evaluation was performed on the skin texture. The sensory evaluation was evaluated as an average score of five panelists according to the following criteria in comparison with the commercially available light liquid detergent Akron (registered trademark). Very excellent +2 points Excellent +1 point Equal 0 points Inferior -1 point Obviously inferior -2 points.

(3) Evaluation of storage stability The components shown in Table 1 were mixed by a batch method to prepare a liquid detergent having a pH of 7.0. Each of the obtained liquid detergents was evaluated for storage stability as described below. <Storage stability> The sample was transferred to a screw tube (diameter 4 cm, height 10
cm), and stored at 50 ° C., room temperature, and −5 ° C., respectively. Twenty days after each storage, the presence or absence of consolidation, separation, and precipitation was visually determined, and the following evaluation was performed. ：: Uniform and transparent liquid under all temperature conditions. X: An opaque liquid or solidification, separation or precipitation occurred under any temperature conditions.

[0032]

[Table 1]

(Note) * Polymer 1: K salt of polyacrylic acid (Mw6,000) * Polymer 2: Penten / maleic acid (50/50 molar ratio)
Na salt of copolymer (Mw 7,000) * Polymer 3: diisobutylene / maleic acid (50/50 molar ratio) Na salt of copolymer (Mw 7,000) * Polymer 4: K salt of polyacrylic acid (Mw 60,000) * Non Ionic surfactant 1: Palm kernel oil fatty acid (C6-18) monoethanolamide * Nonionic surfactant 2: Palm kernel oil fatty acid (C6-18) diethanolamide * Nonionic surfactant 3 : In the general formula (I), R ¹ is an alkyl group having 12 carbon atoms, R ² is an alkylene group having 2 carbon atoms,
Compound in which m is 2 and n is 0 * Nonionic surfactant 4: a polyoxyethylene alkyl ether obtained by adding an average of 3 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms in the alkyl group * Non-ionic surfactant Ionic surfactant 5: a polyoxyethylene alkyl ether obtained by adding an average of 5 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms in the alkyl group * Nonionic surfactant 6: polyoxyethylene lauryl ether * Nonionic surfactant 7: a polyoxyethylene alkyl ether having an alkyl group having 12 to 14 carbon atoms and an average of 7 moles of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms. * Nonionic surfactant 8: alkyl glucoside
The alkyl group has 8 to 14 carbon atoms and a glucose condensation degree of 1.3 * Alkyl benzene sulfonate: The alkyl group carbon number is
12-13, monoethanolamine salt * Alkyl ether sulfate: alkyl group having 12 carbon atoms, ethylene oxide added on average 4 mol,
Monoethanolamine salt * Dialkylammonium chloride: alkyl group having 16 to 18 carbon atoms * Silicone 1: The following general formula (IV)

[0034]

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Wherein l is from 100 to 600, and m and n are numbers such that l: n = 100: 1 and m: n = 1: 1-10 to 10: 1.

R: an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group or an alkoxy group R ¹ : an alkyl group having 1 to 4 carbon atoms, which may be different from each other.

A: a group represented by the following (A) or a group represented by the following (A) and (B); in the latter case, the proportion of (B) in A is 50 mol% or less.

[0038]

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A: 2 to 6 R ² : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms p: 1 to 6 q: 1 to 20 r: 0 to 20 R ³ : an alkyl group having 1 to 18 carbon atoms B: _{- (CH 2) a -O- (} C 2 H 4 O) x - (C 3 H 6 O) y -R 4 or R ¹ R ^4: an alkyl group having 1 to 20 carbon atoms x: 20 y: 0 to 20 is indicated. ] Is the following compound.

R: CH ₃ R ¹ : CH ₃ A: (a) — (CH ₂ ) ₃ —NH—CO—CH ₂ —O— (CH ₂ CH ₂ O) ₅ —C ₁₂ H ₂₅ and ( _II ) ) - (CH2) ₃ mixture of -NH ₂ [(a) / (b) = 7/3 (molar ratio)] _{B :-( CH 2) 3 -O- (} CH 2 CH 2 O) 10 -CH 3 l: 300 m: 7 n: 4 * Silicone 2: The compound in the above general formula (IV) is the following compound.

R: CH ₃ R ¹ : CH ₃ A: — (CH ₂ ) ₃ —NH—CO—CH ₂ —O— (CH ₂ CH ₂ O) ₅ —C ₁₂ H ₂₅ B: —CH ₃ l: 300 m: 7 n: 4

Claims (2)

[Claims] (1) 0.1 to 10% by weight of an unsaturated carboxylic acid oligomer having an average molecular weight of 500 to 50,000, and (b) 0.5 to 10% by weight of a nonionic surfactant represented by the following general formula (I). % Liquid detergent composition containing 5 to 70% by weight of a surfactant other than (c) and (b). <(B): Nonionic surfactant (I)> R ¹ CON (R ² O) _m H (R ³ O) _n H (I) (wherein, R ¹ is a straight or branched chain carbon number of 4 represents an alkyl group or alkenyl group of ~20, R ^2, R ³ is 2 carbon atoms
4 to 4 alkylene groups. m and n have a value of 0 to 5, 1
It is the number of moles of alkylene oxide added so that ≦ m + n ≦ 7. ) 2. The liquid detergent composition according to claim 1, wherein the component (c) is an anionic surfactant having alkanolamine as a counter ion.