JP2006199856A - Liquid detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothing, capable of imparting flexibility to the clothing after washing it, preferably obtaining moderate viscosity excellent in applying property in the vicinity of neutral state and also having good stability over time. <P>SOLUTION: This liquid detergent composition for clothing is characterized by containing (A) a nonionic surfactant, (B) a nitrogen-containing compound of a tertiary amine having an 8-28C hydrocarbon group which may have a substituent or a linkage group in its chain and/or its salt and (C) a polymer having a specific urethane group. Also, the liquid detergent composition for clothing preferably contains 5-50 mass% (A) the nonionic surfactant, 0.1-10 mass% (B) the nitrogen-containing compound and 0.1-20 mass% (C) the polymer having the urethane group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  Conventionally, various liquid detergent compositions for clothing have been proposed.

For example, Patent Documents 1 to 8 and the like disclose detergent compositions in which various blending ratios of nonionic surfactant / anionic surfactant / monoalkyl cationic surfactant are specified.
Patent Documents 9 and 10 also disclose a cleaning agent using an amine compound and a surfactant in combination.
Furthermore, Patent Document 11 proposes a laundry detergent composition containing a primary amine, secondary amine, tertiary amine, and lipolytic enzyme, and particularly exhibiting high cleaning properties against oils and fats and oil stains. Yes.
Patent Document 12 proposes to impart high viscosity by a combination of an anionic surfactant and an amidoamine salt.
JP 56-152898 A JP 56-152899 A JP-A-61-97396 Japanese Patent Application Laid-Open No. 61-60796 JP 62-223299 A Japanese Unexamined Patent Publication No. 62-70498 JP-A-7-166190 JP-A-10-88187 JP-T63-500104 JP-A-10-72772 Japanese National Patent Publication No. 10-509468 Japanese National Patent Publication No. 15-82387

By the way, the liquid detergent composition for clothing is required to have a function of imparting comfortable flexibility to the washed-out clothing in order to improve the comfort at the time of wearing, in addition to the cleaning function of removing dirt.
In addition, it is desired that the liquid has an appropriate viscosity from the viewpoint of usability such as ease of application of the liquid detergent to clothing. For example, if the viscosity is too low, there is a problem that it cannot be applied to the target part, and conversely, if the viscosity is too high, the discharge from the container is inconvenient, and the amount of the composition finally remaining in the container is large. turn into.

In particular, detergents for delicate textile materials such as wool, silk, acrylic, and the like, and so-called light detergents, so-called light detergents, have a moderate viscosity and moderate viscosity from the standpoint of flexibility and ease of application after washing. It is desired to be sex.
Further, a stable characteristic that hardly changes in viscosity during storage is desired.
However, no conventional liquid detergent composition for clothing has been proposed that satisfies all of these characteristics.

Moreover, as a general thickener which gives a viscosity to a liquid detergent composition, an acrylic acid type thickener, a hydroxy cellulose type thickener, etc. are mentioned.
However, since the acrylic acid thickener thickens in the alkaline region, the thickening effect is small in the vicinity of neutrality, so it is difficult to obtain an appropriate viscosity.
In addition, the hydroxycellulose-based thickener tends to decrease in viscosity due to storage over time under high temperature conditions.

  Therefore, even if a conventionally known thickener is simply applied, as described above, the effect of imparting flexibility, preferably imparting an appropriate viscosity in the vicinity of neutrality, and stability over time, should be satisfied. I can't.

  The present invention has been made in view of the above circumstances, and can impart flexibility to clothes after washing, preferably an appropriate viscosity excellent in applicability in the vicinity of neutrality, and stability over time. It is an object of the present invention to provide a good liquid detergent composition for clothing.

As a result of intensive studies, the present inventors have found that the above problems can be solved by blending together a specific nitrogen-containing compound and a polymer having a specific urethane group, and have completed the present invention.
That is, the liquid detergent composition for clothing of the present invention may have a nonionic surfactant (A) and a substituent, and may have a linking group in the chain. A nitrogen-containing compound (B) which is a tertiary amine having a hydrocarbon group of ˜28 and / or a salt thereof, and a polymer (C) having a urethane group represented by the following formula (I): Features.

(In the above formula (I), R ₁ is a linear or branched alkyl or alkenyl group having 10 to 22 carbon atoms, and each R ₁ may be the same or different. R ₂ Represents a linear or branched alkyl group or alkenyl group having 1 to 10 carbon atoms, X and Y each represent one or more alkylene oxides having 2 to 4 carbon atoms, and m and n each represent 10 to 10 carbon atoms. Indicates an integer of 150.)

  Moreover, the liquid detergent composition for clothes of this invention contains 5-50 mass% of said nonionic surfactant (A), and contains 0.1-10 mass% of said nitrogen-containing compound (B). It is preferable to contain 0.1-20 mass% of the polymer (C) having the urethane group.

  According to the present invention, a liquid detergent composition for clothes that can impart flexibility to clothes after washing, preferably has an appropriate viscosity with excellent applicability in the vicinity of neutrality, and has good stability over time. Things can be provided.

  Hereinafter, the present invention will be described in detail.

"Nonionic surfactant (A)"
The nonionic surfactant (A) is a component mainly responsible for a cleaning function, and may be used alone or in combination of two or more.
The nonionic surfactant (A) used in the present invention is not particularly limited. For example, a polyoxyalkylene type nonionic surfactant represented by the following formula (II) is preferably used.

However, in the above formula (II), R ₃ is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms.
Preferred examples of the hydrophobic group include alkyl groups and alkenyl groups, which may be linear or branched. Examples of the raw material used for introducing the hydrophobic group include primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.
R ₄ is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a hydrogen atom.
-M- is a linking group, preferably -O-, -COO-, or -CONH-, more preferably -O-.
EO is ethylene oxide and PO is propylene oxide. α and β represent the average number of moles added. α is 3 to 20, preferably 5 to 18, and more preferably an integer of 5 to 15. β is 0-6, preferably 0-3.
By setting the average added mole number α of EO to 20 or less, it is possible to suppress a decrease in cleaning function due to disadvantageous cleaning of sebum due to HLB becoming too high, and the average added mole number α of EO is 3 or more. In addition, by making the average added mole number β of PO 6 or less, it is possible to suppress a decrease in storage stability of the composition at a high temperature.

The added mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant (A), 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 group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

As specific examples of the nonionic surfactant (A) represented by the above formula (II),
(I) Made by Mitsubishi Chemical Co., Ltd .: Trade name Diadol (C13 (indicating carbon number of 13; hereinafter, similarly, “Cn” (n is an integer) indicates that the carbon number is n.)) , Manufactured by Sasol: synthetic alcohol obtained by the oxo method such as trade name Safol23 (C12 / C13 mixture), or manufactured by P & G Co., Ltd .: product name CO-1214 (C12 / C14 mixture), manufactured by Eco Green Oleochemicals: product A product obtained by adding 15 moles of ethylene oxide to a natural alcohol such as Ecolol (C12 / C14 mixture) (ii) Shin Nippon Rika Co., Ltd .: natural alcohol such as Conol (C12) (Iii) C13 alkene obtained by subjecting C12 alkene obtained by trimerization of butene to oxo method 7 mol or 10 mol equivalent of ethylene oxide is added to 1 mol of coal (BASF, trade name: Lutensol TO7, Lutensol TO10)
(Iv) 15 moles of ethylene oxide added to lauric acid methyl ester (v) 10 moles of ethylene oxide added to 1 mole of C12 alcohol obtained by subjecting hexanol to garvet reaction Things (made by CONDEA: trade name ISOFOL12-10EO)
(Vi) A product obtained by adding 15 moles of ethylene oxide to C12-14 secondary alcohol (manufactured by Nippon Shokubai Co., Ltd .: trade name Softanol 150)
(Vii) A compound obtained by adding 15 moles of ethylene oxide and 3 moles of propylene oxide to methyl laurate using an alkoxylation catalyst.

As the component (A), the nonionic surfactant represented by the above formula (II) is described as suitable, but other nonionic surfactants can also be used.
Other nonionic surfactants suitable for use include, for example, polyoxyethylene (EO addition mole number 1-20) sorbitan fatty acid (C10-22) ester, polyoxyethylene (EO addition mole number 1-20). Examples include sorbite fatty acid (C10-22) ester, polyoxyethylene (EO addition mole number 1-20) glycol fatty acid (C10-22) ester, glycerin fatty acid (C10-22) ester, alkyl (C10-22) glycoside and the like. .

These components (A) may be used individually by 1 type, or may use 2 or more types together.
In the present invention, the compounding amount of component (A) (when two or more types are used in combination, it means the total amount. The same applies to other components described later). 50 mass% is preferable, 6-45 mass% is more preferable, and 7-40 mass% is especially preferable. The detergency is improved by setting the blending amount of the component (A) to 5% by mass or more, and the viscosity of the composition is prevented from excessively increasing by setting it to 50% by mass or less. The stability of is improved.

"Nitrogen-containing compounds (B)"
In the composition of the present invention, the nitrogen-containing compound (B) may be linear or branched, saturated or unsaturated, and further has a substituent. The hydrocarbon group having 8 to 28 carbon atoms (the carbon number here does not include the substituent and the carbon number in the linking group) which may have a linking group in the chain is 1 to A tertiary amine containing 3 and / or a salt thereof is blended. In particular, a tertiary amine containing 1 to 3, preferably 1 to 2 hydrocarbon groups having 8 to 25 carbon atoms and / or a salt thereof is blended.
Here, the “substituent” specifically includes a hydroxy group, an amino group, and the like.
Specific examples of the “linking group” include an amide group, an ester group, and an ether group.
Specific examples of tertiary amines and / or salts thereof include those using tertiary amines as they are, and acid salts obtained by neutralizing tertiary amines with acids.
Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. Two or more types may be used in combination.

  As the nitrogen-containing compound (B), a tertiary amine represented by the following formula (III) and / or a salt thereof is particularly suitable.

In the above formula (III), R ₅ is a hydrocarbon group having 8 to 27 carbon atoms (the carbon number here does not include the carbon number in the substituent and the linking group), It may be branched, may be saturated or unsaturated, and may further contain a substituent. R ₅ may have a linking group such as an amide group, an ester group or an ether group in its chain, and an amide group or an ester group is preferably used as the linking group.
Among them, R ₅ is “—R ₈ —W” (where R ₈ is a linear or branched alkylene group having 1 to 4 carbon atoms. W is —NHCO—R ₉ or —OOC—R ₁₀ . R _{9 and} R ₁₀ are hydrocarbon groups having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated. Is also preferred.

R ₆ is a hydrocarbon group having 1 to 25 carbon atoms. R ₆ may be linear or branched, may be saturated or unsaturated, and may further contain a substituent. R ₆ may have a linking group such as an amide group, an ester group or an ether group in the chain.
Of these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are preferably used.

R ₇ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and a polyoxyethylene group having 1 to 25 moles of EO addition. And a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is preferably used.

  Among the above formulas (III), tertiary amines represented by the following formula (IV) and / or salts thereof are more preferable.

However, in the above formula _{(IV), R 11, R} 12 are each a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.
R ₁₃ is a linear or branched alkylene group having 1 to 4 carbon atoms.
Z is a group represented by the following formula (V) or (VI).

However, in the above formulas (V) and (VI), R ₁₄ and R ₁₅ are each a hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms. It may be saturated or unsaturated.

Preferable specific examples of component (B) include lauric acid amidopropyl dimethylamine, myristic acid amidopropyl dimethylamine, palmitic acid amidopropyl dimethylamine, stearic acid amidopropyl dimethylamine, behenic acid amidopropyl dimethylamine, oleic acid amide. Long-chain aliphatic amidoalkyl tertiary amines such as propyldimethylamine or salts thereof; aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; or salts thereof; amidopropyl diethanolamine palmitate, And stearic acid amidopropyl diethanolamine.
Of these, myristic acid amidopropyl dimethylamine, palmitic acid amidopropyl dimethylamine, stearic acid amidopropyl dimethylamine, behenic acid amidopropyl dimethylamine, oleic acid amidopropyl dimethylamine or salts thereof are particularly preferable.

The “long-chain aliphatic amidoalkyl tertiary amine” in the above examples is a dehydration of a fatty acid or a fatty acid derivative such as a fatty acid lower alkyl ester or animal / vegetable oil and fat and a dialkyl (or alkanol) aminoalkylamine. It is obtained by carrying out a condensation reaction and then distilling off unreacted dialkyl (or alkanol) aminoalkylamine under reduced pressure or nitrogen blowing.
On the other hand, the “aliphatic ester alkyl tertiary amine” is obtained, for example, by an esterification reaction in which a fatty acid or a fatty acid lower alkyl ester, a fatty acid derivative such as animal or vegetable oil and fat, and a dialkylamino alcohol are subjected to dehydration condensation.

Here, as the fatty acid or fatty acid derivative, 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, corn oil fatty acid, beef tallow fatty acid , Palm kernel fatty acid, soybean oil fatty acid, linseed 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., specifically, 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.
Examples of “dialkylamino alcohol” include dimethylaminoethanol, diethylaminoalcohol and the like. As the diethylamino alcohol, diethylaminoethanol is preferable. Among these, dimethylaminoethanol 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 is too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored, which is not preferable.

As for the usage-amount of the dialkylamino alcohol in esterification reaction at the time of manufacturing aliphatic ester alkyl tertiary amine, 0.1-5.0 times mole is preferable with respect to a fatty acid or its derivative (s), and 0.3-3. A 0-fold mole is particularly preferred.
The reaction temperature is usually 100 to 220 ° C, preferably 120 to 180 ° C. If the reaction temperature is less than 100 ° C., the reaction is too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored, which is not preferable.

The production conditions of the long-chain aliphatic amidoalkyl tertiary amine and aliphatic ester alkyl tertiary amine other than those described above are the same, and the pressure during the reaction may be normal pressure or reduced pressure, and an inert gas such as nitrogen is blown during the reaction. It is also possible to introduce it.
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.

  Other suitable specific examples of component (B) include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, hardened tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, Examples include polyoxyethylene-cured tallow alkylamine (product name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.), or salts thereof.

These components (B) may be used individually by 1 type, or may use 2 or more types together.
In this invention, 0.1-10 mass% is preferable in a composition, as for the compounding quantity of a component (B), 0.5-8 mass% is more preferable, and 0.5-5 mass% is especially preferable. By making the blending amount of the component (B) 0.1% by mass or more, an effect of imparting flexibility to the clothing can be obtained. On the other hand, when the blending amount of the component (B) is 10% by mass or less, the effect of imparting flexibility to clothing can be sufficiently obtained, and it is economically advantageous.

[Polymer having urethane group (C)]
The polymer (C) having a urethane group used in the present invention is a polymer having a urethane group represented by the above formula (I).

In the above formula (I), R ₁ has 10 to 22 carbon atoms, preferably 12 to 20 carbon atoms, and more preferably a linear or branched alkyl group or alkenyl group having 14 to 20 carbon atoms. . Each R ₁ may be the same or different.
R ₂ represents a linear or branched alkyl group or alkenyl group having 1 to 10 carbon atoms.

X and Y each represent one or more alkylene oxides having 2 to 4 carbon atoms. Especially, it is preferable that each of X and Y consists of two types of alkylene oxide, and it is more preferable that these two types of alkylene oxides are a combination of ethylene oxide having 2 carbon atoms and propylene oxide having 3 carbon atoms. .
m and n each represent an integer of 10 to 150, preferably 10 to 100.
Moreover, it is preferable that m + n is 20-100, and it is more preferable that m + n is 50-90.
The alkylene oxide content in the polymer (C) having a urethane group is 0.1 to 20% by mass, preferably 0.5 to 15% by mass, and more preferably 0.5 to 12% by mass.
When the content of alkylene oxide is 0.1% by mass or more, a thickening effect is obtained, and when the content of alkylene oxide is 20% by mass or less, stability over time is improved.

Such a polymer (C) having a specific urethane group mainly contributes to the viscosity adjustment of the liquid detergent composition for clothing of the present invention, and can improve the applicability of the composition to clothing.
As a viscosity, the viscosity of the composition in 30 degreeC is 50-5000 mPa * s, 50-3000 mPa * s is preferable and 50-2000 mPa * s is more preferable. By setting the viscosity of the composition to 50 mPa · s or more, an appropriate viscosity can be obtained, the persistence of the composition when the composition is applied to clothing is improved, and the viscosity of the composition is 5000 mPa · s or less. This improves the permeability to clothing and improves the coating effect.
In addition, a viscosity can be adjusted with the kind of component (C), the compounding quantity of a component (C), etc.

A component (C) may be used individually by 1 type, or may use 2 or more types together.
In this invention, 0.1-20 mass% is preferable in a composition, as for the compounding quantity of a component (C), 0.2-15 mass is more preferable, and 0.5-15 mass% is especially preferable. By setting the blending amount of the component (C) to 0.1% by mass or more, an appropriate viscosity can be obtained, and the stability over time is improved. On the other hand, the blending amount of the component (C) is set to 20% by mass or less. This improves the coating effect and also improves the stability over time.

The composition of the present invention essentially comprises the above components (A) to (C), but in addition to these components, other optional components are blended as necessary within the range not impairing the effects of the present invention. can do.
Other ingredients that can be blended include, for example, enzymes (proteases, lipases, cellulases, etc.), stabilizers (sodium benzoate, citric acid, sodium citrate, Hydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene polypropylene glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, polypropylene glycol phenyl ether, polyethylene polypropylene glycol phenyl ether, etc.), texture improver, pH adjuster, preservative , Hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents and the like can be blended.

In the composition of this invention, it is preferable to set it as pH 4-9 from the point which maintains the favorable stability at the time of storing a composition for a long period of time, and pH 4-8 is more preferable.
What is necessary is just to mix | blend a pH adjuster suitably in order to adjust pH to 9 or less. As a pH adjuster, as long as the effect of the present invention is not impaired, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of blending stability.

Furthermore, a hydrotrope agent is preferably used for the purpose of further improving the stability over time.
Examples of the hydrotrope include alcohols, sulfonic acids having 4 to 10 carbon atoms in the molecule, and aromaticity, or salts thereof.
As a specific example, ethanol is used as the alcohol.
In addition, sulfonic acid or a salt thereof containing 4 to 10 carbon atoms in the molecule and having aromaticity is benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, sulfobenzoic acid, sulfophthalic acid. , Naphthalenesulfonic acid and its sodium salt, potassium salt, diethanolamine salt and the like. Among these, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid and its sodium salt, potassium salt, and diethanolamine salt are preferable, and it is more preferable to use in combination with ethanol.

Furthermore, a texture improver can be blended for the purpose of improving the texture when worn.
Examples of the texture improver include polyether-modified silicone and amino polyether-modified silicone. These may be used individually by 1 type, or may use 2 or more types together, As a preferable compounding quantity, it is 0.1-3 mass%.

In addition, a coloring agent, a flavoring agent, an emulsifying agent, etc. can also be mix | blended for the purpose of the added value improvement of goods, etc.
As the colorant, 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, and Turquoise P-GR (both trade names) can be used. A preferable blending amount is about 0.00005 to 0.0005 mass%.
As a typical example of the flavoring agent, perfume compositions A, B, C, and D described in Tables 6 to 13 of JP-A-2003-206495 can be used. % By mass.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. As a specific example, a polystyrene emulsion (product name: Cybinol RPX-196 PE-3, solid content 40%, manufactured by Seiden Chemical Co., Ltd.) can be used, and a preferable blending amount is 0.01 to 0.5% by mass. is there.

  The liquid cleaning composition for clothing of the present invention is not particularly limited in its preparation method, and in the same manner as a normal liquid cleaning composition, for example, the above essential components and, if necessary, the above It can be prepared by blending optional components and water as appropriate and mixing them.

The liquid detergent composition for clothes of the present invention can be used by filling a resin container such as a plastic container.
For example, examples of the plastic container include a bottle main body container and a standing pouch for refilling.
As a bottle main body container, what was described in Unexamined-Japanese-Patent No. 2001-3100 or Japanese Patent Application No. 2002-71756 is preferable.
Examples of the standing pouch include those described in JP-A No. 2000-72181. As this material, an inner layer / outer layer double layer structure in which linear low density polyethylene of 100 to 250 μm is used for the inner layer and stretched nylon of 10 to 30 μm is employed for the outer layer, or stretched nylon of 10 to 15 μm is employed for the intermediate layer. A standing pouch with a three-layer structure of inner layer / intermediate layer / outer layer that employs one or more of stretched propylene resin and stretched polyethylene terephthalate resin and stretched nylon of 10-15 μm in the outer layer has good stability over time It is preferable from the point of keeping.

  The method of using the composition of the present invention is not particularly limited, and it may be washed by hand or by a washing machine. For example, in the case of washing with a normal washing machine, after the article to be washed is put into the washing machine, the washing machine tub is filled with water, and the composition of the present invention is added to an appropriate concentration and dissolved. Thus, the washing liquid can be obtained, and thereby the washing object can be washed.

According to the present invention, since the constitution in which the nonionic surfactant (A), the nitrogen-containing compound (B) and the polymer having a urethane group (C) are blended is adopted, the clothes after washing are flexible. It is possible to provide a liquid detergent composition for clothing that preferably has a moderate viscosity excellent in applicability near neutral and has good stability over time. Also, a cleaning function for removing dirt can be obtained.
Furthermore, since it is not necessary to use an anionic surfactant as a main base material, it is excellent in productivity and economically advantageous. Moreover, it can be conveniently used like a normal liquid detergent for clothing.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by the Example described below.
In addition, the unit of the compounding quantity in a table | surface shows the mass%. In the following description, “%” related to the blending amount and concentration is “% by mass” unless otherwise specified.

(Examples 1-17 and Comparative Examples 1-9)
In each example, a liquid cleaning composition for clothing was prepared in the same manner except that the blending composition was changed, and each was evaluated. The composition of each example is shown in Tables 1-3.

In the table, only the component (A), the component (B), the component (C), and the component (D) for comparison are described. Each liquid detergent composition for clothing was prepared by a conventional method. In accordance with components (A) to (C) or (D), common components were blended in the following composition, and each composition was obtained by appropriately adjusting the amount of water so that the total of all components was 100% by mass. .
Moreover, it adjusted using either sulfuric acid, sodium hydroxide, monoethanolamine, or an oxalic acid (all are manufactured by Kanto Chemical) as a pH adjuster so that pH of a composition might become what is shown to the same table | surface.
In addition, in the common component, the blending amount of each component indicates the blending amount as a whole (total amount), and the blending amount of components other than the common component indicates a pure conversion amount.

<Common ingredients>
Fragrance 0.2% by mass
Isothiazolone solution 0.01% by mass
Dye 0.0003 mass%
Emulsifier 0.225% by mass
pH adjuster appropriate amount water balance

In the common component, details of each component are as follows.
Isothiazolone solution: Rohm and Haas (trade name) Kaisson CG-ICP (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / Water mixture)
Dye (Acid Red 138): Sumitomo Chemical Co., Ltd. (trade name) Suminol Milling Brilliant Red BS
Emulsifying agent: Syden Chemical Co., Ltd. (trade name) Cybinol (RPX-196) PE-3
pH adjuster: sulfuric acid or sodium hydroxide perfume: perfume compositions A to D described in Tables 6 to 13 of JP-A-2003-206495

Moreover, the following compound was used as a component (A).
(A-1): C _n H _{2n + 1} O (EO) ₁₅ H (n = 12/14 mixture (mass ratio 7/3)), manufactured by Ecogreen (trade name) KB-15, CO12-14 alcohol mean EO15 mol adduct _{(a-2): C n} H 2n + 1 O (EO) 15 H (n = 12/14 mixture (weight ratio 7/3)), Ecogreen (Ltd.) (trade name) KB-5, CO12-14 alcohols average EO5 mole adduct _{(a-3): C 13} H 27 O (EO) 5 H (C chain length: branched), BASF Corp. (trade name) Lutensol TO5
(A-4): C ₁₃ H ₂₇ O (EO) ₇ H (C chain length: branched type), manufactured by BASF (trade name) Lutensol TO7
(A-5): C ₁₃ H ₂₇ O (EO) ₁₀ H (C chain length: branched type), manufactured by BASF (trade name) Lutensol TO10
(A-6): C ₁₃ H ₂₇ O (EO) ₃ H (C chain length: branched type), manufactured by BASF (trade name) Lutensol TO3

The following compounds were used as the component (B).
_{(B-1): C 11} H 23 CONH (CH 2) 3 N (CH 3) 2, Lion Co., synthetic _{(b-2): C 13} H 27 CONH (CH 2) 3 N (CH _{3) 2,} Lion Co., synthetic _{(b-3): C 15} H 31 CONH (CH 2) 3 N (CH 3) 2, Lion Co., synthetic (b-4): C _{17 H 35 CONH (CH 2)} 3 N (CH 3) 2, Lion Co., synthetic _{(b-5): C 17} H 33 CONH (CH 2) 3 N (CH 3) 2, Lion (strain ), Synthetic product (b-6): C ₂₁ H ₄₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , manufactured by Lion Corporation, synthetic product (b-7): C ₁₅ H ₃₁ COONH (CH ₂₎ ) ₃ N _{(CH 3) 2,} Lion Co., synthetic _{(b-8): C 15 31 CONH (CH 2) 2 N} (CH 3) 2, Lion Co., synthetic _{(b-9): C 15} H 31 CONH (CH 2) 3 N (C 2 H 4 OH) 2, Lion ( Co., Ltd., synthesized product (b-10): C _n H _{2n + 1} CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (n = 15/17 mixture (mass ratio 3/7)), manufactured by Toho Chemical Co., Ltd. (Product Name) Kachinar MPAS-R

The following compounds were used as the component (C).
_{(C-1): C 16/18} - (EO) 60 (PO) 14 -CONH- (CH 2) 6 -NHCO- (P
O) ₁₄ (EO) _60- C _16/18 , manufactured by AKZO NOBEL (trade name) Elfacos T
212

Moreover, the following component (D) was used for the comparison of a component (C).
(D-1): Acrylic acid polymer, manufactured by Rohm and Haas (trade name) ACUSOL 820
(D-2): Hydroxyethyl cellulose, manufactured by Daicel Chemical Industries (trade name) HEC SE200

Next, the manufacturing method of a synthetic product is shown below.
(B-1):
Into a 1 liter four-necked flask, 261 g of lauric acid is charged and nitrogen substitution is performed at 80 ° C.
I went twice. The temperature was raised to 170 ° C., and 173 g of dimethylaminopropylamine was added dropwise over 2 hours while distilling off by-product water.
After completion of dropping, the mixture was kept at 170 to 180 ° C. and aged for 7 hours. The conversion rate of lauric acid calculated from the acid value was 99%.
After aging, the pressure was reduced to remove unreacted amine and water to obtain (b-1).

(B-2):
Synthesis was performed in the same manner as in (b-1) except that 298 g of myristic acid was used instead of lauric acid. The conversion of myristic acid calculated from the acid value was 99%.
(B-3):
Synthesis was performed in the same manner as in (b-1) except that 334 g of palmitic acid was used instead of lauric acid. The conversion of palmitic acid calculated from the acid value was 99%.
(B-4):
Synthesis was performed in the same manner as (b-1) except that 370 g of stearic acid was used instead of lauric acid. The conversion rate of stearic acid calculated from the acid value was 99%.
(B-5):
Synthesis was performed in the same manner as (b-1) except that 368 g of oleic acid was used instead of lauric acid. The conversion rate of oleic acid calculated from the acid value was 99%.
(B-6):
Synthesis was performed in the same manner as (b-1) except that 444 g of behenic acid was used instead of lauric acid. The conversion rate of behenic acid calculated from the acid value was 99%.

(B-7):
A 1-liter four-necked flask was charged with 386 g of methyl palmitate, 200 g of dimethylaminoethanol, and 2 g of p-toluenesulfonic acid as a catalyst, and was purged with nitrogen twice. A dehydration condensation reaction was carried out at a reaction temperature of 140 to 150 ° C. for 10 hours while distilling off by-produced methanol. The conversion rate of methyl palmitate calculated from the saponification value was 99%.
Thereafter, the pressure was reduced and unreacted dimethylaminoethanol and methanol were distilled off to obtain (b-7).

(B-8):
The compound was synthesized in the same manner as (b-1) except that 334 g of palmitic acid was used instead of lauric acid and 149 g of dimethylaminoethylamine was used instead of dimethylaminopropylamine. The conversion of palmitic acid calculated from the acid value was 99%.
(B-9):
Synthesis was performed in the same manner as in (b-1) except that 334 g of palmitic acid was used instead of lauric acid and 275 g of diethanolaminopropylamine was used instead of dimethylaminopropylamine. The conversion of palmitic acid calculated from the acid value was 99%.

(Evaluation methods)
Hereinafter, the evaluation method will be described, and the obtained evaluation results are shown in Tables 1 to 3.

<Evaluation of viscosity of composition>
In a 200 ml beaker, 200 ml of the liquid detergent composition for clothing prepared in each example was put, and the viscosity at 30 ° C. was measured with a B-type viscoclock No. 2 rotor at a rotation speed of 60 rpm.

<Evaluation of flexibility>
Seven sheets of commercially available T-shirts (100% cotton, manufactured by BVD) were put into a two-tub washing machine, and 30 L of tap water and 40 mL of a liquid detergent composition for clothing prepared in each example were added.
Then, a washing operation was performed in which the washing time (10 minutes), dehydration (1 minute), and subsequent rinse (repeated twice / 5 minutes each) and dehydration (1 minute) were performed in one step with a weak water flow.
The temperature of the tap water used was adjusted to 25 ° C. Moreover, the free chlorine concentration of the tap water used for experiment was 0.5 ppm.
The T-shirt treated by the washing operation was shaded and dried for 12 hours. Then, it was left in a constant temperature and humidity room of 25 ° C./65% RH (humidity) for 2 days, and this was used as a test garment for evaluation of flexibility.
As an evaluation control garment, a T-shirt washed as described above using a 20% by mass aqueous solution of a nonionic surfactant (alcohol ethoxylate added with an average of 15 mol of ethylene oxide per mol of lauryl alcohol). Using.
Flexibility was evaluated by ten expert panelists based on sensuality.
The evaluation method was carried out by comparing one pair of test clothing and control clothing, and obtaining the average value of 10 professional panelists based on the following criteria.
The evaluation criteria are shown below.
1 point: Equivalent to control clothing 2 points: Slightly softer than control clothing 3 points: Softer than control clothing 4 points: Much softer than control clothing 5 points: Very softer than control clothing

<Evaluation of stability over time>
150 ml of liquid detergent composition for clothing was filled into a cylindrical glass bottle having a diameter of 50 mm and a height of 100 mm, and the lid was closed and sealed.
In this state, after storage for 1 month in a constant temperature bath at 50 ° C. and −5 ° C., the appearance of the composition was visually observed and evaluated according to the following criteria.
The evaluation criteria are shown below.
1 point: Remarkable precipitation was observed 2 points: Precipitation was observed 3 points: Some precipitation was observed 4 points: No change in appearance was observed except for very slight precipitation 5 points: Change in appearance Was not recognized at all

(Evaluation results)
As shown in each table, a nonionic surfactant (A), a tertiary amine having a hydrocarbon group having 8 to 28 carbon atoms and / or a nitrogen-containing compound (B) which is a salt thereof, and a urethane group The composition of each example blended with the polymer (C) having the above can impart flexibility to the clothes after washing, obtain an appropriate viscosity excellent in applicability, and has good stability over time. there were.
On the other hand, in Comparative Examples 7 to 9 that did not contain the component (B) among the components (A), (B), and (C), the evaluation of flexibility was low.
Moreover, about Comparative Examples 1-6 which mix | blended the component (D) instead of the component (C), the viscosity of the composition was low in Comparative Examples 1-3. In Comparative Examples 4 to 6, the stability over time was poor.
From the above results, it was confirmed that the effects of the present invention were exhibited by containing the components (A), (B), and (C).

Claims (2)

A nonionic surfactant (A), a tertiary amine having a hydrocarbon group having 8 to 28 carbon atoms, which may have a substituent and may have a linking group in the chain, and / or A liquid detergent composition for clothing comprising a nitrogen-containing compound (B) as a salt thereof and a polymer (C) having a urethane group represented by the following formula (I).

(In the above formula (I), R ₁ is a linear or branched alkyl or alkenyl group having 10 to 22 carbon atoms, and each R ₁ may be the same or different. R ₂ Represents a linear or branched alkyl group or alkenyl group having 1 to 10 carbon atoms, X and Y each represent one or more alkylene oxides having 2 to 4 carbon atoms, and m and n each represent 10 to 10 carbon atoms. Indicates an integer of 150.)   The nonionic surfactant (A) is contained in an amount of 5 to 50% by mass, the nitrogen-containing compound (B) is contained in an amount of 0.1 to 10% by mass, and the polymer (C) having the urethane group is added in an amount of 0.0. It contains 1-20 mass%, The liquid cleaning composition for clothes of Claim 1 characterized by the above-mentioned.