JP2013057011A - Liquid detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothing which can prevent a liquid detergent from yellowing while improving a flexible effect by containing an amino-modified silicone.SOLUTION: The liquid detergent composition for clothing contains (A) 0.01-5 mass% of an amino-modified silicone compound and (B) 0.5-30 mass% of urea, a double salt or derivative thereof, wherein (A)/(B)=0.01/12 to 5/1 (mass ratio).

Description

  The present invention relates to a liquid detergent composition for clothing.

In recent years, detergents for wool and dry mark clothing have been widely used not only for sweaters but also for cut-and-sew, underwear and shorts. Good finish is one of the requirements for these light detergents. So far, it has been reported that amino-modified silicone is used as a means for enhancing the finishing feeling of a neutral liquid detergent for household use including a light detergent, particularly a softening effect (Patent Documents 1 to 3).
However, there is a problem that the liquid detergent itself turns yellow by blending amino-modified silicone. In liquid detergents, fragrance and liquid color may be related to consumer feelings, and it is necessary to change the liquid color according to the purpose during development. Therefore, changing the liquid color over time has been a problem of narrowing the selection range of the liquid color. Therefore, in the present invention, a liquid detergent composition that further improves the finish feeling and prevents liquid yellowing by using amino-modified silicone is established.

JP 2010-059275 A JP 2000-178600 A Japanese Patent Laid-Open No. 10-060480

  An object of the present invention is to provide a liquid detergent composition for clothing that can prevent yellowing of a liquid detergent while increasing the softening effect on an object to be washed by including an amino-modified silicone.

According to the present invention, (A) amino-modified silicone compound: 0.01 to 5% by mass,
(B) Urea, double salt or derivative thereof: 0.5 to 30% by mass
Containing
Provided is a liquid detergent composition for clothing in which (A) / (B) = 0.01 / 12 to 5/1 (mass ratio).

  According to the present invention, there is provided a liquid detergent composition for clothing that has a softening effect higher than that of a conventional neutral liquid detergent for household clothing and that suppresses yellowing of the liquid detergent itself.

(A) Amino-modified silicone compound The amino-modified silicone compound used in the present invention is a silicone oil in which amino groups are introduced at both ends or side chains of a dimethyl silicone skeleton.
The amino-modified silicone compound used in the present invention preferably has a kinematic viscosity at 25 ° C. of 100 to 20000 mm ² / s, and more preferably 500 to 10,000 mm ² / s. A kinematic viscosity in this range is preferable because the manufacturability is good and the composition is easy to handle. The kinematic viscosity can be measured with an Ostwald viscometer.
The amino-modified silicone compound used in the present invention preferably has an amino equivalent of 100 to 10,000, more preferably 1200 to 4000. An amino equivalent in this range is preferable because flexibility is good. The amino equivalent is determined by dividing the weight average molecular weight by the number of nitrogen atoms. The number of nitrogen atoms is determined by elemental analysis.
The amino-modified silicone compound used in the present invention is preferably water-insoluble. In this specification, “water-insoluble” means that the amount dissolved in 1 L of water at 25 ° C. is 10 g or less.

As the amino-modified silicone oil, commercially available ones can be used. For example, BY16-871 as a both-end modified type, BY16-893, BY-891 as a side chain-modified type from Toray Dow Corning Co., Ltd. , And those sold as FBN-3789 as ABN type.
By containing the component (A), better flexibility can be imparted to the object to be washed than when the POE-modified silicone is contained.
(A) Content of a component is 0.01-5 mass% with respect to the total mass of the composition of this invention, Preferably it is 0.1-3 mass%. By setting it as 0.01 mass% or more, the compounding effect of (A) component fully expresses. On the other hand, even if the blending amount of the component (A) is more than 5% by mass, no further effect is obtained and the yellowing of the liquid detergent composition becomes severe.

(B) Urea, double salt or derivative thereof As urea double salt in the present invention, HNO ₃ · CO (NH ₂ ) ₂ , H ₃ PO ₄ · CO (NH ₂ ) ₂ , H ₂ C ₂ O ₄ · ₂ CO _{(NH 2) 2, Ca (} NO 3) 2 · 4CO (NH 2) 2, CaSO 4 · 4CO (NH 2) 2, Mg (NO 3) 2 · CO (NH 2) 2 · 2H 2 O, CaSO 4 (5-6) 4CO (NH ₂ ) ₂ .2H ₂ O and the like.
The “urea derivative” in the present invention is represented by the following formula (1).

In formula (1), ^Ra is a methyl group, an ethyl group, or a C1-C2 hydroxyalkyl group. R ^b , R ^c and R ^d are each independently a hydrogen atom, a methyl group or an ethyl group.
Examples of the compound represented by the formula (1) include 1,3-dimethylurea and N- (2-hydroxyethyl) urea. Of these, 1,3-dimethylurea is preferred.
As the component (B), one type may be used alone, or two or more types may be used in combination. As the component (B), urea is preferable.
By adding the component (B) in the liquid detergent, yellowing of the liquid detergent caused by the amino-modified silicone can be prevented.
(B) Content of a component is 0.5-30 mass% with respect to the total mass of the composition of this invention, Preferably it is 1-10 mass%, More preferably, it is 1-8 mass%. If the content of the component (B) is less than the lower limit, yellowing of the liquid washing product may not be suppressed. On the other hand, if the content exceeds the upper limit, ammonia tends to be generated as a decomposition product after storage, resulting in a liquid detergent. Odor may be a problem as a product. Moreover, since the affinity to dirt tends to decrease, there is a risk that the cleaning power will decrease.
The blending ratio of these components (A) and (B) is 0.01 / 12 to 5/1 in terms of mass ratio (A) / (B), preferably 0.01 / 1 to 1/1. . Outside this range, a sufficient effect for suppressing yellowing of the detergent cannot be obtained.

The liquid detergent composition for clothing of the present invention is made into a liquid composition by dissolving the above components (A) and (B) in water which may contain a water-miscible organic solvent.
In addition to the essential components (A) and (B) described above, the liquid detergent composition for clothing of the present invention further contains the following components that are usually used in liquid detergent compositions for clothing. As long as the effect is not impaired, it can be included as needed.

(C) Lactic acid or its salt Examples of the lactate include alkali metal salts and alkanolamine salts of lactic acid. In particular,
CH ₃ CH (OH) COO ⁻ .Na ⁺ ,
CH ₃ CH (OH) COO ⁻ · K ⁺ ,
CH ₃ CH (OH) COO ^−. (NH ₃ C ₂ H ₄ OH) ⁺
Etc. can be used.
(C) As a component, the alkali metal salt of lactic acid is preferable. Sodium lactate is more preferred.
By blending the component (C), irritation to the skin by the component (B) is alleviated. Although details are unknown, it is thought that component (C) adheres to the skin and blocks the stimulation of component (B).
As for content of (C) component in this invention, 0.5 mass%-15 mass% are preferable with respect to the total mass of a composition, More preferably, it is 1-10 mass%, More preferably, it is 2-5 mass. %. If the content of the component (C) is less than the lower limit value, stimulation by urea cannot be covered, and even if the content exceeds the upper limit value, an effect commensurate with it cannot be obtained, which is economically disadvantageous.
The blending ratio of the component (B) and the component (C) is preferably 0.5 / 15 to 10/1 in terms of mass ratio (B) / (C), and more preferably 0.5 / 15 to 1/1. . If it is outside this range, a sufficient effect in suppressing irritation to the hand skin cannot be obtained.

(D) Surfactant (D) By adding a component, detergency and a softness | flexibility can further be provided to the liquid detergent composition of this invention.
(D-1) Nonionic surfactant (D-1) A component can be mix | blended mainly for the purpose of further providing detergency to the liquid detergent composition for clothes of this invention.
Although it does not specifically limit as nonionic surfactant (D-1) which can be used by this invention, For example, the polyoxyalkylene type nonionic surfactant represented by following General formula (2) is suitable. Used.
R2-X- (EO) n (PO) m-R3 (2)
In the formula, R 2 is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and may be linear or branched. Specific examples of the hydrophobic group include those derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like. -X- is a functional group such as -O-, -COO-, -CONH-.
EO is ethylene oxide and PO is propylene oxide.
n and m represent an average number of added moles, n is 3 to 20, preferably 5 to 18, and m is 0 to 6, preferably 0 to 3.

R3 is a hydrogen atom or an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms.
If the average added mole number n of EO exceeds 20, the HLB (according to the Griffin equation) becomes too high and disadvantageous for the sebum cleaning, so that the cleaning function is lowered. Therefore, it is preferable that HLB is 6-20. Odor deterioration can be prevented when the average added mole number n of EO is 3 or more. If the average added mole number m of PO exceeds 6, the storage stability of the liquid detergent composition at a high temperature tends to decrease, which is not preferable. In particular, when an ethylene group and a propylene group are contained, the addition method of ethylene oxide and propylene oxide may be, for example, random addition or addition of ethylene oxide followed by addition of propylene oxide, and vice versa. But you can.
The width of the addition mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant represented by the formula (2), and is not particularly limited. For example, the addition mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Then, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-615038 were added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide, the distribution tends to be relatively narrow.

In Formula (2), when -X- is -O-, the component (D-1) is an alcohol ethoxylate. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R2 is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. R2 may have an unsaturated bond. In this case, R3 is preferably a hydrogen atom.
In the formula (2), when -X- is -COO-, the component (D-1) is a fatty acid ester type nonionic surfactant. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R2 is 9 to 21, preferably 11 to 21. R2 may have an unsaturated bond. In this case, R3 is preferably an alkyl group having 1 to 3 carbon atoms.
As the nonionic surfactant represented by the formula (2), an alcohol ethoxylate in which -X- is -O- is preferable.

  Specific examples of the nonionic surfactant represented by the formula (2) include: Mitsubishi Chemical Co., Ltd .: trade name Diadol (C13, C represents the number of carbons; the same shall apply hereinafter), Shell: trade name Neodol (C12 / C13), manufactured by Sasol: alcohol obtained by adding 12 and 15 moles of ethylene oxide to alcohol such as Safol23 (C12 / C13), manufactured by P & G: trade names CO-1214 and CO-1270, etc. 1,12 and 15 moles of ethylene oxide added to natural alcohol, C12 alkene obtained by triming butene to 5 moles, and 7 moles of ethylene oxide in C13 alcohol obtained by subjecting to oxo method C1 obtained by subjecting pentanol to gerbet reaction (additional product manufactured by BASF: trade name: Lutensol TO5, TO7) 5 mol, 7 mol equivalent ethylene oxide added to alcohol (BASF: Lutensol XA50, XA70), 5 mol, 7 mol equivalent ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (BASF: Lutensol XL50, XL70), C10 alcohol obtained by subjecting pentanol to the garvet reaction, 5 mol, 7 mol equivalent propylene oxide, and ethylene oxide added (BASF: Lutensol XP50) , XP70) What is obtained by adding ethylene oxide corresponding to 3 mol, 5 mol, 7 mol to a secondary alcohol having 12 to 14 carbon atoms (manufactured by Nippon Shokubai Co., Ltd., Softanol 30, 50, 70), and the like. Furthermore, what added the ethylene oxide of 9 mol and 15 mol to the palm fatty acid methyl (lauric acid / myristic acid = 8/2) using the alkoxylation catalyst is mentioned.

Examples of nonionic surfactants other than the nonionic surfactant represented by the formula (2) include alkylene oxide adducts such as alkylphenols, higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, Fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl Examples thereof include polyhydroxy fatty acid amides and alkyl glycosides.
As the component (D-1), a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination.
(D-1) The compounding quantity of a component becomes like this. Preferably it is 10-50 mass% with respect to the total mass of the liquid detergent composition for garments, More preferably, it is 10-40 mass%. A high detergency can be given to the liquid detergent composition for clothes as it is 10 mass% or more. High stability can be given to the liquid detergent composition for clothes as it is 50 mass% or less.

(D-2) Anionic surfactant The anionic surfactant (D-2) in the present invention has an SO ₃ group or an SO ₄ group, which are known substances, and are easily marketed. It can be obtained.
Specific examples of the component (D-2) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt An alkane sulfonate having an alkyl group; an α-sulfo fatty acid ester salt;
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
Further, the following are preferable as the anionic surfactant having these SO ₃ groups or SO ₄ groups.
In the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.

The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (that is, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
The carbon number of the alkane sulfonate is 10 to 20, preferably 14 to 17, and the secondary alkane sulfonate is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
Among the above specific examples, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are preferable.
As the component (D-2), a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.

The anionic surfactant having an SO ₃ group or an SO ₄ group as the component (D-2) is blended mainly for the purpose of imparting anti-contamination performance and ensuring the storage stability of the component (D-1). . The amount of anionic surfactant having an SO ₃ group or SO ₄ groups, based on the total weight of the clothing the liquid detergent composition is preferably 0 to 20 wt%.
Examples of other anionic surfactants include carboxylic acids such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. Examples thereof include phosphoric acid ester type anionic surfactants such as types, alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts and glycerin fatty acid ester monophosphoric acid ester salts.

(D-3) Cationic surfactants Cationic surfactants can be used as those that further impart flexibility, but tertiary amine compounds are particularly preferred in terms of high flexibility and high storage stability. preferable.
The tertiary amine compound is a compound represented by the following formula (3).

In the formula, R4 is a hydrocarbon group having 7 to 27 carbon atoms which may have a substituent and / or a linking group (in the case of having a substituent and / or a linking group, Is not included in the carbon number here). R5 and R6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of EO addition. is there).
The carbon number of the hydrocarbon group of R4 (when having a substituent and / or linking group, the carbon number in the substituent and / or linking group is not included in the carbon number here) is 7 to 27, preferably It is C7-25. R4 may be linear or branched and may be saturated or unsaturated. R4 may have a linking group such as an amide group, an ester group or an ether group in the chain.
Among the compounds represented by the formula (3), tertiary amine compounds represented by the following formula (4) or the following formula (5) and / or salts thereof are preferable.

  In the formula, R7 may be linear or branched, and may be a saturated or unsaturated hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21 carbon atoms. R8 is a linear or branched alkylene group having 1 to 4 carbon atoms. R9 and R10 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of EO addition. .

In the formula, R11 may be linear or branched, and is a hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms, which may be saturated or unsaturated. R12 is a linear or branched alkylene group having 1 to 4 carbon atoms. R13 and R14 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of EO addition. .
Specific examples of the tertiary amine compound include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl. Long-chain aliphatic amide dialkyl tertiary amines (compounds represented by formula 4) such as amide, dimethylaminopropylamide behenate, dimethylaminopropylamide oleate or salts thereof; palmitate ester propyldimethylamine, stearate ester propyldimethyl Aliphatic ester dialkyl tertiary amines such as amines (compounds represented by formula 5) or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanol Such as amino propyl amide. Among them, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide Particularly preferred is dimethylaminopropylamide oleate or a salt thereof.

The production of the tertiary amine compound will be described using the “long-chain aliphatic amide alkyl tertiary amine” in the above examples. For example, fatty acids or fatty acid lower alkyl esters, fatty acid derivatives such as animal and vegetable oils and fats, , Dialkyl (or alkanol) aminoalkylamine is subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing. Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or their methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable. These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.
Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.
In addition, the amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 moles relative to the fatty acid or derivative thereof. 0 to 1.5 times mole is particularly preferable. The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction becomes too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
The production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine can be appropriately changed. The pressure during the reaction may be normal pressure or reduced pressure, and may be introduced by blowing an inert gas such as nitrogen during the reaction. Is possible.

Also, when using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when using fatty acid derivatives, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed efficiently.
Further, when the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.
Furthermore, as a specific example of the above-mentioned tertiary amine marketed, Toho Chemical Co., Ltd. Katchinal MPAS-R etc. are mentioned.

Other specific examples of the tertiary amine compound that can be used as the component (D-3) include lauryl dimethylamine, myristyl dimethylamine, coconut alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, cured tallow alkyl dimethylamine, Stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hydrogenated beef tallow alkylamine (trade name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.), and the like.
Specific examples of the tertiary amine compound include those using the tertiary amine as they are, acid salts obtained by neutralizing the tertiary amine with an acid, and the like. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid and the like, and these are used alone. Or you may use 2 or more types together.
The tertiary amine as the component (D-3) is blended mainly for the purpose of imparting softness performance to clothes after washing such as cotton to the liquid detergent composition for clothing of the present invention.

(D) The compounding quantity of a component becomes like this. Preferably it is 0.1-10 mass% with respect to the total mass of the liquid detergent composition for garments, More preferably, it is 0.5-5 mass%. When the content is 0.1% by mass or more, a softening effect is obtained on the washed clothes, and at the same time, a slipping effect due to the component (A) is sufficiently exhibited. Even if blending more than 10% by mass, the effect of improving the flexibility is not seen, which is disadvantageous economically.
In terms of flexibility, the blending ratio of the component (C) and the component (D) is desirably 0.5 / 10 to 15 / 0.1 in terms of mass ratio. More preferably, the ratio is 1/1 to 10/1.
Examples of other cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant. Is mentioned.

(E) Water-miscible organic solvent Alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, glycols such as propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Water such as polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, polyethylene glycol having a weight average molecular weight of about 1000, polyglycols such as dipropylene glycol, alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether For example, the miscible organic solvent can be contained in an amount of 0.1 to 15% by mass.

For example, 0.01 to 30% by mass of a stabilizer such as paratoluenesulfonic acid and benzoate (which also has an effect as a preservative) can be contained.
For example, 0.1 to 20% by mass of a metal ion sequestering agent such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid or citric acid can be contained.
An antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite can be contained, for example, in an amount of 0.01 to 2% by mass.
A preservative such as an isothiazolone solution (for example, Caisson CG (trade name) manufactured by Rohm and Haas) can be contained, for example, in an amount of 0.001 to 1% by mass.

Furthermore, for the purpose of improving cleaning performance and stability, enzymes (proteases, lipases, cellulases, etc.), texture improvers, alkali builders such as alkanolamines, pH adjusters, hydrotropes, fluorescent agents, dye transfer inhibitors , A recontamination inhibitor such as a copolymer of maleic acid and an olefin monomer, a pearl agent, a soil release agent, and the like.
In addition, flavoring agents, coloring agents, emulsifying agents, natural products, and the like can also be included for the purpose of improving the added value of goods.
As typical examples of the flavoring agent, the fragrance compositions A, B, C, and D described in Tables 11 to 18 of JP-A-2002-146399 and Table 1 of Japanese Patent Application No. 2007-283650 are described. Perfume compositions a, b, c and d can be used, and the preferred blending amount is 0.1 to 1% by mass.
General-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names) For example, about 0.00005 to 0.005 mass%.

Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion. Usually, an emulsion having a solid content of 30 to 50% by mass is suitably used. As a specific example, polystyrene emulsion (Syden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be contained in an amount of 0.01 to 0.5% by mass.
Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, Liquidambar formosana, Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plants such as St. John's wort, these example, can include about 0-0.5 wt%.

The liquid detergent composition for clothing of the present invention preferably has a pH of 4 to 9 at 25 ° C., more preferably 4 to 8. When the pH is in such a range, precipitation does not occur and the storage stability is excellent. The pH adjuster that can be used in the present invention is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, and the like are preferable from the viewpoint of stability.
The technique of the present invention can be widely used not only for liquid detergent compositions for clothing but also for wrinkle sprays containing amino-modified silicone compounds, softeners, shampoos, rinses, conditioners and the like.

[Preparation of liquid detergent composition for clothing]
A liquid detergent composition for clothing having the composition shown in Table 1 was prepared as follows.
(1) A 300 mL beaker was charged with the silicone compound (A) in ethanol in the following common components, and sufficiently stirred with a magnetic stirrer (MITAMURA KOGYO INC.).
(2) Add the surfactant (C) to (1), stir well, and then add the water in the common component at 40 ° C, then add the component (B) dissolved in ethanol beforehand And fully dissolved.
(3) The remaining components and common components were added to (2) and stirred well, and the pH was adjusted to 7 with a small amount of aqueous sodium hydroxide solution to obtain a liquid detergent composition for clothing. The pH was measured at 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).

As the component (A), the following water-insoluble silicone compound was used.
(A-1) Amino-modified silicone, manufactured by Toray Dow Corning Co., Ltd. Trade name: BY16-893, kinematic viscosity 550 mm ² / s, amino equivalent 4000
(A-2) Amino-modified silicone manufactured by Toray Dow Corning Co., Ltd. Trade name: FZ-3789, kinematic viscosity 1000 mm ² / s, amino equivalent 1200
(A-3) Amino-modified silicone, manufactured by Toray Dow Corning Co., Ltd. Trade name: BY16-891, kinematic viscosity 750 mm ² / s, amino equivalent 3000
Comparison (a-4) Polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd. Product name: SH3775M, kinematic viscosity 630 mm ² / s
Comparison (a-5) Polyether-modified silicone of the general formula (6) wherein, m = 210, n = 9 , R1 = C 3 H 6, X = - (OC 2 H 4) 10-, in R = CH ₃ A silicone compound, synthetic product, kinematic viscosity 5300 mm ² / s.

Synthesis of (a-5) was performed as follows.
In a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet, 100 g of an organohydrogenpolysiloxane (α = 210, β = 9) represented by the following formula (7), isopropyl alcohol 50 g, 29 g of a polyoxyalkylene compound (d = 10, G = CH ₃ ) represented by the following formula (8), 0.2 g of an addition reaction catalyst, and 0.3 g of an isopropyl alcohol solution of 2% by mass sodium acetate were added. These were reacted at 90 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain (a-5).

As the component (B), the following compounds were used.
(B-1) Pure Chemical Industries, Ltd. Product name: Urea (special grade)
(B-2) Tokyo Chemical Industry Co., Ltd. trade name: 1,3-dimethylurea

As the component (C), the following compounds were used.
(C) Wako Pure Chemical Industries, Ltd. Product name: Sodium lactate

As the component (D), the following compounds were used. (The HLB value is calculated from the Griffin equation)
(D-1) A product obtained by adding 12 moles of ethylene oxide to P & G natural alcohol CO-1270 (HLB: 15)
(D-2) A product obtained by adding 15 moles of ethylene oxide to P & G natural alcohol CO-1270 (HLB: 15)
(D-3) A product obtained by adding 10 moles of ethylene oxide to P & G natural alcohol CO-1270 (HLB: 14)
(D-4) Coconut fatty acid methyl (lauric acid / myristic acid = 8/2) added with 15 moles of ethylene oxide using an alkoxylation catalyst, synthetic product (HLB: 15)
(D-5) Coconut fatty acid methyl (lauric acid / myristic acid = 8/2) added with 9 mol of ethylene oxide using an alkoxylation catalyst, synthetic product (HLB: 13)
(D-6) Nippon Shokubai Co., Ltd. product name Softanol 30 (HLB: not disclosed)
(D-7) Nippon Shokubai Co., Ltd. product name Softanol 50 (HLB: not disclosed)
(D-8) Product name manufactured by BASF: Lutenzol TO5 (HLB: not disclosed)
(D-9) Product name manufactured by BASF: Lutenzol TO7 (HLB: not disclosed)
In addition, the common component in a table | surface shows the following compositions.

<Common component a>
Sodium benzoate 0.5% by mass
Citric acid 0.13 mass%
95% ethanol 7.0% by mass (including the amount used to dissolve component B)
P-Toluenesulfonic acid 1.3% by mass
Isothiazolone solution 0.01% by mass
Sodium salt of copolymer of maleic acid and olefinic monomer 0.5% by mass
Stearic acid dimethylaminopropylamide 1.25% by mass
Fragrance 0.3% by mass
Water balance (amount to make the total amount of detergent composition 100 parts)

<Common component b>
Sodium benzoate 0.5% by mass
Citric acid 0.13 mass%
95% ethanol 8.0% by mass (including the amount used to dissolve component B)
Paratoluenesulfonic acid 4.0% by mass
Polyethylene glycol 1.5% by mass
Isothiazolone solution 0.01% by mass
Sodium salt of copolymer of maleic acid and olefinic monomer 0.5% by mass
Amidoamine 2.5% by mass
Fragrance 0.6% by mass
Water balance (amount to make the total amount of detergent composition 100 parts)

In the common component, details of each component are as follows.
Sodium benzoate: Toagosei Co., Ltd. Product name Sodium benzoate Trisodium citrate: Miles (USA) Product name Sodium citrate 95% ethanol: Nippon Alcohol Sales Co., Ltd. Product name Specific alcohol 95 degree synthesis Paratoluenesulfonic acid : Kyowa Hakko Kogyo Co., Ltd. Product name PTS acid Polyethylene glycol: Lion Co., Ltd. product name “PEG # 1000-L60”
Isothiazolone solution: Rohm and House, Inc., trade name Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture)
Sodium salt of copolymer of maleic acid and olefinic monomer: manufactured by BASF Ltd. Product name: Socaran CP9 (molecular weight 12000)
Amidoamine: manufactured by Toho Chemical Co., Ltd. Product name: Kachinal MPAS-R
Perfume ingredient a described in Japanese Patent Application No. 2007-283650

〔Evaluation method〕
The following evaluation was performed using the liquid detergent composition prepared above. However, no evaluation was performed on samples that had precipitated or become cloudy in the initial appearance.
(1) Flexibility evaluation In a fully automatic electric washing machine (JW-Z23A manufactured by Haier), three commercially available cotton towels (100% cotton) and a bath ratio (washing water / washed cloth total mass) increased by 25 times In order to adjust, two cotton shirts (made by BVD, total wash cloth mass about 420 g) were added, and 16 mL of liquid detergent composition for clothing shown in Tables 1 and 2 was added. In the standard course, washing operations were performed in order of washing, rinsing and dehydration. With regard to washing time, rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L), no adjustment was made and the soft course setting of the washing machine was used.
After the washing was completed, the taken out towel was left in a constant temperature and humidity room at 25 ° C. and a humidity of 65% RH to dry. This was used as a test cloth for flexibility evaluation.
A test except that 16 mL of 20% nonionic surfactant (a product obtained by adding ethylene oxide equivalent to 15 moles to natural alcohol CO-1270 manufactured by P & G: d-2) was used as an evaluation control cloth. A cotton towel treated in the same way as the cloth was used.
For the evaluation of the softening effect, a pairwise comparison was made on the control cloth according to the following evaluation criteria by sensory sense, and the average value of five professional panelists was obtained.
<Evaluation criteria>
5 points: Very softer than control cloth 4 points: Much softer than control cloth 3 points: Softer than control cloth 2 points: Slightly softer than control cloth 1 point: Equivalent to control cloth Pass if the above average value is 3 points or more It was.
◎: 4 points or more, ○: 3 points or more and less than 4 points, △: 2 points or more and less than 3 points, ×: less than 2 points

(2) Stability over time 100 mL of the liquid detergent composition prepared above was prepared as a test sample.
As an evaluation control sample, a 20% nonionic surfactant (a product obtained by adding ethylene oxide equivalent to 15 mol to natural alcohol CO-1270 manufactured by P & G: d-2) was prepared.
These test sample and evaluation control sample were each taken in a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, it was placed in a constant temperature bath at 40 ° C. and stored for 1 month, and then the appearance of the liquid was visually observed. One pair comparison was performed according to the following evaluation criteria, and the average value of five professional panelists was obtained.
<Evaluation criteria>
3 points: equivalent to the control sample 2 points: slightly yellowish than the control sample 1 point: yellowish than the control sample The case where the above average value was 2.5 points or more was regarded as acceptable.
○: 2.5 to 3 points, Δ: 2 to less than 2.5 points, ×: less than 2 points

(3) Odor Evaluation of Formulation As a test sample, 100 mL of the liquid detergent composition prepared above was prepared.
As an evaluation control sample, a 20% nonionic surfactant (a product obtained by adding ethylene oxide equivalent to 15 mol to natural alcohol CO-1270 manufactured by P & G: d-2) was prepared.
These test samples and evaluation control samples were each taken in transparent glass bottles (wide-mouth standard bottle PS-NO.11), and the same fragrance was added by 0.3 mass%.
One pair comparison was made by the sensory evaluation according to the following evaluation criteria with respect to this evaluation control detergent, and the average value of five professional panelists was obtained.
3 points: Equivalent to the control sample 2 points: Smells somewhat from the control sample 1 point: Smells from the control sample The case where the average value is 2.5 points or more was regarded as acceptable.
○: 2.5 to 3 points, Δ: 2 to less than 2.5 points, ×: less than 2 points

(4) Hand skin touch evaluation during hand washing A test sample prepared by dissolving 25 mL of the liquid detergent composition prepared above in 5 L of water was prepared.
As an evaluation control sample, 20% nonionic surfactant (a product obtained by adding 15 mol equivalent of ethylene oxide to natural alcohol CO-1270 manufactured by P & G: d-2) 25 mL dissolved in 5 L of water Prepared.
One hand was put on these test samples, the other hand was put on the evaluation control sample, and after 5 minutes, the hands were rinsed with tap water.
The feeling received in the hand by sensory evaluation was compared with the following evaluation criteria, and the average value of five professional panelists was obtained.
<Evaluation criteria>
5 points: considerably better than the evaluation sample 4 points: slightly better than the evaluation sample 3 points: equivalent to the evaluation sample 2 points: slightly worse than the evaluation sample 1 point: considerably worse than the evaluation sample

The case where the said average value was 3 or more points was set as the pass.
◎: 4 points or more, ○: 3 points or more and less than 4 points, △: 2 points or more and less than 3 points, ×: less than 2 points

Claims (5)

(A) Amino-modified silicone compound: 0.01 to 5% by mass,
(B) Urea, double salt or derivative thereof: 0.5 to 30% by mass
Containing
(A) / (B) = 0.01 / 12-5 / 1 (mass ratio) liquid detergent composition for clothes.   Furthermore, (C) Lactic acid or its salt: The liquid detergent composition for clothes of Claim 1 containing 0.5-15 mass%.   The liquid detergent composition for clothing according to claim 2, wherein (C) is sodium lactate. Urea double salt is HNO ₃ · CO (NH ₂ ) ₂ , H ₃ PO ₄ · CO (NH ₂ ) ₂ , H ₂ C ₂ O ₄ · ₂ CO (NH ₂ ) ₂ , Ca (NO ₃ ) ₂ · 4CO (NH ₂ ) ₂ , CaSO ₄ · 4CO (NH ₂ ) ₂ , Mg (NO ₃ ) ₂ · CO (NH ₂ ) ₂ · 2H ₂ O, CaSO ₄ · (5-6) 4CO (NH ₂ ) ₂ · 2H _The liquid detergent composition for clothes according to any one of claims 1 to 3, which is selected from the group consisting of 2O. The liquid detergent composition for clothing according to any one of claims 1 to 3, wherein the urea derivative is represented by the following formula (1).

(In the formula, R ^a is a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms. R ^b , R ^c, and R ^d are each independently a hydrogen atom, a methyl group, or an ethyl group. .)