JP2009179745A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition exhibiting such an excellent effect that an object to be cleaned is restrained from being fluffed. <P>SOLUTION: The liquid detergent composition comprises a nonionic surfactant (A) and 0.1-5 mass% at least one cationic polymer compound (B) selected from the group consisting of cationized cellulose and cationized guar gum. It is preferable that the liquid detergent composition further comprises a nitrogen-containing compound (C) being tertiary amine, which has a 7-28C hydrocarbon group (on condition that the hydrocarbon group may have a substituent and a linking group in the chain thereof), and/or its salt. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

In general, in washing using a washing machine at home, it is known that fluffing occurs in the washing object due to rubbing or entanglement of the washing object such as clothing during washing.
Due to the effect of the fluff, in the washed object after washing, so-called “whitening” occurs in which the reflected light increases and the washed object itself appears whitish.

Until now, as a method of suppressing the fluff of the washing object, for example, a method using a cellulase preparation containing a polymer has been proposed. Specifically, a cellulase preparation containing a specific terephthalic acid-alkylene glycol copolymer or a terephthalic acid-oligoalkylene glycol copolymer alone or in combination with an endoglucanase having a cellulose binding domain (CBD), and the cellulase preparation A detergent composition obtained by blending a product with a detergent component has been proposed (see Patent Document 1).
JP 2002-142760 A

However, in the conventional cleaning composition such as Patent Document 1, there is a problem that in order to obtain a sufficient effect of suppressing fluffing in the article to be cleaned, a large amount of components exhibiting such an effect must be blended. The effect of suppressing fuzz is still not satisfactory.
In the present specification, the “effect of suppressing fluff” refers to an effect of delaying the start of fluffing of the fibers of the article to be washed, an effect of reducing the degree of fluffing of the fibers, an effect of preventing fibers from fluffing, etc. It shall be included.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the liquid detergent composition excellent in the effect which suppresses the fluff in to-be-washed | cleaned material.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent composition of the present invention comprises a nonionic surfactant (A) and at least one cationic polymer compound (B) selected from the group consisting of cationized cellulose and cationized guar gum. 5 mass% is contained, It is characterized by the above-mentioned.

In the liquid detergent composition of the present invention, a hydrocarbon group having 7 to 28 carbon atoms (however, the hydrocarbon group may have a substituent and a linking group in the chain). It is preferable to further contain a nitrogen-containing compound (C) which is a tertiary amine and / or a salt thereof.
In the liquid detergent composition of the present invention, the mixing ratio [(B) / (C)] of the cationic polymer compound (B) and the nitrogen-containing compound (C) is 1 in mass ratio. A range of / 10 to 1/1 is preferable.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition excellent in the effect which suppresses the fuzz in a to-be-washed | cleaned object can be provided.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises at least one cationic polymer compound selected from the group consisting of nonionic surfactant (A) (hereinafter referred to as component (A)), cationized cellulose and cationized guar gum. In the liquid detergent composition of the present invention containing 0.1 to 5% by mass (hereinafter referred to as component (B)), a hydrocarbon group having 7 to 28 carbon atoms (however, the hydrocarbon group) Is a tertiary amine having a substituent and may have a linking group in its chain) and / or a nitrogen-containing compound (C) (hereinafter referred to as (C) It is preferable to further contain a component)).

<(A) component>
In the present invention, the component (A) is a nonionic surfactant.
By containing the component (A), a cleaning effect is mainly obtained.

The component (A) is not particularly limited. For example, polyoxyethylene sorbitan fatty acid ester (preferably one having 1 to 20 added moles of ethylene oxide and 10 to 22 carbon atoms of fatty acid), polyoxyethylene Sorbit fatty acid ester (preferably having 1 to 20 moles of added ethylene oxide, 10 to 22 carbon atoms of fatty acid), polyoxyethylene glycol fatty acid ester (preferably having 1 to 20 moles of added ethylene oxide, carbon number of fatty acid) 10 to 22), glycerin fatty acid ester (preferably fatty acid having 10 to 22 carbon atoms), alkyl glycoside (preferably alkyl having 10 to 22 carbon atoms), represented by the following general formula (1) And polyoxyalkylene type nonionic surfactants.
Among these, the polyoxyalkylene type nonionic surfactant represented by the following general formula (1) is preferable because both the detergency and the effect of suppressing fuzz in the article to be washed are good.

［式中、Ｒ^１は炭素数８〜２２の疎水基であり、Ｒ^２は水素原子又は炭素数１〜６のアルキル基もしくは炭素数２〜６のアルケニル基であり、−Ｙ−は連結基を示し、ＥＯはオキシエチレン基を示し、ＰＯはオキシプロピレン基を示す。ｍおよびｎはいずれも平均付加モル数を表し、ｍは３〜２０の数であり、ｎは０〜６の数である。］

[Wherein, R ¹ is a hydrophobic group having 8 to 22 carbon atoms, R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, and —Y— is a linking group. EO represents an oxyethylene group, and PO represents an oxypropylene group. m and n both represent the average number of moles added, m is a number from 3 to 20, and n is a number from 0 to 6. ]

In the general formula (1), R ¹ is a hydrophobic group having 8 to 22 carbon atoms, and preferably a hydrophobic group having 10 to 16 carbon atoms.
In R ¹ , the hydrophobic group is preferably an alkyl group or an alkenyl group, which may be linear or branched.
In the synthesis of the compound represented by the above formula (1), examples of the raw material used for introducing the hydrophobic group include primary higher alcohols, secondary higher alcohols, higher fatty acids, higher fatty acid amides and the like. .

R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
In R ² , the alkyl group preferably has 1 to 3 carbon atoms, and may be linear or branched. Further, the alkenyl group preferably has 2 to 3 carbon atoms, and may be linear or branched.
Among these, as ^{R 2,} a hydrogen atom is more preferable.

  -Y- represents a linking group, preferably -O-, -COO-, or -CONH-, more preferably -O-.

EO represents an oxyethylene group, and PO represents an oxypropylene group.
m and n both represent the average number of moles added.
m is a number of 3 to 20, preferably a number of 5 to 18, and more preferably 5 to 15.
n is a number from 0 to 6, and preferably a number from 0 to 3.
By setting m to 20 or less, it is possible to prevent deterioration of the cleaning function due to disadvantageous cleaning of sebum due to an excessively high HLB value. Further, when m is 3 or more and n is 6 or less, the storage stability of the liquid detergent composition at high temperature can be improved.

In the compound represented by the above formula (1), the distribution of the number of moles of ethylene oxide or propylene oxide is not particularly limited and can be controlled by the reaction method during the production of the component (A).
For example, the addition mole number distribution of ethylene oxide or propylene oxide 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 alkoxyl such as magnesium oxide added with 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 JP-B-615038 When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

Specific examples of the compound represented by the formula (1) include (i) to (vii) shown below.
(I) Oxo such as Sasol 23 manufactured by Sasol (mixture of 6/4 by mass ratio (C12 / C13) having an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms) A product obtained by adding 15 moles of ethylene oxide to synthetic alcohol obtained by the method;
Equivalent to 15 moles with respect to natural alcohol such as P & G brand name CO-1214 (C12 / C14 mixture), P & G brand name Eco Green, or Oleochemicals brand name Ecolor (C12 / C14 mixture). To which ethylene oxide is added.
(Ii) A product obtained by adding 9 mol of ethylene oxide to a natural alcohol such as trade name Conol (C12) manufactured by Shin Nippon Rika Co., Ltd.
(Iii) 7 moles or 10 moles of ethylene oxide added to 1 mole of C13 alkene obtained by subjecting C12 alkene obtained by trimerizing butene to oxo method (each manufactured by BASF Name Lutensol TO7, trade name Lutensol TO10).
(Iv) 15 mol equivalent of ethylene oxide added to lauric acid methyl ester.
(V) 10 mole equivalent of ethylene oxide added to 1 mole of C12 alcohol obtained by subjecting hexanol to garvet reaction (trade name ISOFOL12-10EO manufactured by CONDEA).
(Vi) 15 mol equivalent of ethylene oxide added to C12-14 secondary alcohol (Nippon Shokubai Co., Ltd .: trade name Softanol 150).
(Vii) A product obtained by adding 15 moles of ethylene oxide and 3 moles of propylene oxide to methyl laurate using an alkoxylation catalyst.

(A) A component can be used individually by 1 type or in mixture of 2 or more types.
The content of the component (A) is preferably 10 to 50% by mass and more preferably 15 to 40% by mass in the liquid detergent composition.
When the content of the component (A) is 10% by mass or more, better detergency can be obtained. (A) It can prevent that the viscosity of a liquid detergent composition increases too much that content of a component is 50 mass% or less, and becomes easy to handle.

<(B) component>
In the present invention, the component (B) is at least one cationic polymer compound selected from the group consisting of cationized cellulose and cationized guar gum.
By containing the said (B) component, the effect which mainly suppresses the fluff in a to-be-washed object is acquired.

The weight average molecular weight of the component (B) is preferably 100,000 to 3,000,000, and more preferably 300,000 to 2,000,000 for both cationized cellulose and cationized guar gum. By being more than the lower limit of the range, the effect of suppressing fuzz in the article to be washed is further improved. On the other hand, if it is below an upper limit, it can prevent that the viscosity of a liquid detergent composition increases too much, and handling becomes easy. In addition, the storage stability of the liquid detergent composition is improved. Furthermore, the solubility of (B) component itself becomes more favorable.
In addition, the weight average molecular weight of (B) component shows the value which analyzed by the gel permeation chromatography (GPC) by making a standard substance into polyethyleneglycol (PEG).

In the component (B), examples of the cationized cellulose include those obtained by adding a cationic functional group to cellulose, and examples of the cationized guar gum include those obtained by adding a cationic functional group to guar gum.
The degree of cationization of the cationized cellulose or the cationized guar gum is preferably in the range of 0.1 to 3.0% by mass, more preferably in the range of 0.4 to 0.8% by mass. preferable. When the cationization degree is within the above range, the effect of suppressing fuzz in the article to be washed is further improved. In addition, the storage stability of the liquid detergent composition is improved.

The degree of cationization in the component (B) can be easily calculated if the chemical structure is clear. Even when the monomer ratio is unknown and the chemical structure is unclear, it can be calculated by measuring the content of nitrogen atom N by the Kjeldahl method or the like.
The “cationization degree” in the present invention is described in the page of Chloride-O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose of Quasi-drug raw material standard 2006 (Pharmaceutical Daily). It can be measured by the method. The nitrogen atom is derived from a cationizing agent, and the degree of cationization can be controlled by adjusting the amount of cationizing agent used.

(Cationized cellulose)
As an example, the cationized cellulose can be produced by reacting hydroxyethyl cellulose obtained by adding ethylene oxide to cellulose and glycidyltrimethylammonium chloride serving as a cationizing agent.

  As a suitable thing of a cationized cellulose, the cationic high molecular compound which has a repeating unit represented with the following general formula (C-1), ie, (halogen) -O- [2-hydroxy-3- (trimethylammoni). O) propyl] hydroxyethylcellulose.

［式（Ｃ−１）中、Ｒ^３〜Ｒ^５は、それぞれ独立して水素原子又は下記式（Ｃ−１−１）で表される基である。ｌ、ｍ、ｎは、それぞれエチレンオキシドの平均付加モル数を示す。］

[In formula (C-1), R ^{3 to} R ⁵ are each independently a hydrogen atom or a group represented by the following formula (C-1-1). l, m, and n each represent the average number of moles of ethylene oxide added. ]

［式（Ｃ−１−１）中、Ｘはハロゲン原子を示す。］

[In the formula (C-1-1), X represents a halogen atom. ]

  In said formula (C-1-1), X shows a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned, A chlorine atom is preferable.

In the cationized cellulose having the repeating unit represented by the formula (C-1), R ^{3 to} R ⁵ are represented by the formula (C) so that the degree of cationization is in the range of 0.1 to 3.0% by mass. It is preferable that it is group represented by C-1-1).

Further, the degree of ethylene oxide (EO) substitution per glucose ring unit is preferably 0.3 to 3.0, and more preferably 0.7 to 2.5.
However, “degree of EO substitution” indicates the average number of hydroxyl groups substituted with EO per glucose ring unit of the cellulose raw material (how many OH groups are added to the three hydroxyl groups of the glucose ring). , A maximum of 3.)

  In the cationized cellulose represented by the formula (C-1), the EO average added mole number per glucose ring unit is preferably 1 + m + n = 1 to 5, and particularly has an effect of suppressing fuzziness in the washing object. Since it is favorable, the lower limit is preferably 1 or more, and the upper limit is more preferably 3 or less.

Specific examples of the cationized cellulose include Leogard LP, GP, MGP, KGP, MLP (all trade names; manufactured by Lion Corporation); UCARE LR-30M, JR-400, JR-30M (all products) Name: Dow Chemical Japan Co., Ltd.); Kachinal HC-100 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
In addition, the difference of the brand name in the said commercially available thing is because the molecular weight of a cellulose, the average addition mole number of EO, a cationization degree, etc. differ.

(Cationized guar gum)
As an example, cationized guar gum can be produced by reacting guar gum with cationizing agent glycidyltrimethylammonium chloride.

  As a suitable cationized guar gum, a cationic polymer compound having a repeating unit represented by the following general formula (C-2), that is, (halogen) -O- [2-hydroxy-3- (trimethylammoni) E) Propyl] guar gum.

［式（Ｃ−２）中、Ｒ’は、それぞれ独立して水素原子又は前記式（Ｃ−１−１）で表される基を示す。ただし、分子内に、少なくとも前記式（Ｃ−１−１）で表される基を有する。］

[In Formula (C-2), R ′ each independently represents a hydrogen atom or a group represented by Formula (C-1-1). However, it has at least a group represented by the formula (C-1-1) in the molecule. ]

In R ′ in the formula (C-2), X in the group represented by the formula (C-1-1) is preferably a chlorine atom.
Moreover, it is preferable that R 'is group represented by the said Formula (C-1-1) in the ratio used as the range of cationization degree 0.1-3.0 mass%.

Specific examples of the cationized guar gum include Laborum gums CG-M, CG-M7, and CG-M8M (all trade names: manufactured by Dainippon Pharmaceutical Co., Ltd.); N-Hance 3000 (trade names, manufactured by Hercules Japan); Commercial products such as Jaguar C-13S, Jaguar C-14S, Jaguar C-17S, Jaguar C-210, Jaguar C-1620 (all trade names; manufactured by Rhone-Poulenc); EXCEL (trade names, manufactured by Rhodia) Is mentioned.
In addition, the difference of the brand name in the said commercially available thing is because the molecular weight or cationization degree, etc. of guar gum differ.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.
Among these, as the component (B), cationized cellulose is preferable because it has a better effect of suppressing fuzz in the object to be washed.
(B) Content of a component is 0.1-5 mass% in a liquid detergent composition, and it is preferable that it is 0.1-2 mass%.
When the content of the component (B) is 0.1% by mass or more, an effect of suppressing fuzz in the article to be washed can be obtained. (B) It can prevent that the viscosity of a liquid detergent composition increases too much that content of a component is 5 mass% or less, and handling becomes easy.

<(C) component>
In the present invention, the component (C) is a hydrocarbon group having 7 to 28 carbon atoms (however, the hydrocarbon group may have a substituent and may have a linking group in the chain). A nitrogen-containing compound which is a tertiary amine and / or a salt thereof.
By using the component (C) and the component (B) in combination, the effect of suppressing fuzz in the article to be washed is synergistically improved.

In the component (C), the hydrocarbon group may be linear or branched, saturated or unsaturated. Specifically, an alkyl group or an alkenyl group is preferable.
The hydrocarbon group may have a substituent and may have a linking group in the chain.
Specific examples of the “substituent” herein include a hydroxy group and an amino group.
Specific examples of the “linking group” include an amide group, an ester group, and an ether group.
In the hydrocarbon group, the carbon number is 7 to 28, preferably 11 to 28, and more preferably 17 to 28. However, the number of carbons here does not include the number of carbons in the substituent and the linking group.
1 to 3 hydrocarbon groups may be contained in the molecule, preferably 1 to 2 and particularly preferably 1 hydrocarbon group.
Specific examples of the component (C) include those using a tertiary amine as it is, and acid salts obtained by neutralizing a tertiary amine with an acid.
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.

  Among the components (C), preferred are compounds represented by the following general formula (2).

［式中、Ｒ^６はアミド基および／もしくはエステル基をその鎖中に有する、炭素数１１〜２８のアルキル基又はアルケニル基であり；Ｒ^７、Ｒ^８はそれぞれ独立に炭素数１〜４のアルキル基又は炭素数１〜４のヒドロキシアルキル基である。］

[Wherein, R ⁶ is an alkyl group or an alkenyl group having 11 to 28 carbon atoms having an amide group and / or an ester group in the chain; R ⁷ and R ⁸ are each independently having 1 to 4 carbon atoms; It is an alkyl group or a C1-C4 hydroxyalkyl group. ]

Specific examples of the compound represented by the general formula (2) include caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic acid amide. Long chain aliphatic amide alkyl tertiary amines such as propyldimethylamine, amidopropyl dimethylamine stearate, amidopropyl dimethylamine behenate, amidopropyl dimethylamine oleate or salts thereof; palmitate ester propyldimethylamine, stearate ester propyl Aliphatic ester alkyl tertiary amines such as dimethylamine or salts thereof; amidopropyl diethanolamine palmitate, amidopropyl diethanolamine stearate, etc. .
Among them, caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic amidopropyl dimethylamine, stearic acid amidopropyl dimethylamine, behenic acid amidopropyl dimethylamine Amines, amidopropyl dimethylamine oleate or salts thereof are preferred, and amidopropyl dimethylamine palmitate and amidopropyl dimethylamine stearate are particularly preferred.

The above “long-chain aliphatic amidoalkyl tertiary amine” is, for example, a condensation reaction of a fatty acid or a fatty acid derivative such as a fatty acid lower alkyl ester or animal / vegetable oil and fat with a dialkyl (or alkanol) aminoalkylamine, and then The unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.
Here, specifically 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, Examples include cottonseed oil fatty acid, 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 or glycerides It is done. Of these, 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 and the like, and 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 fatty acid derivative. 0 to 1.5 times mole is particularly preferable.
The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. When the reaction temperature is 100 ° C. or higher, the reaction does not become too slow and the reaction rate can be controlled, and when it is 220 ° C. or lower, coloring of the resulting tertiary amine can be suppressed, which is preferable.
In the production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine, the reaction pressure may be normal pressure or reduced pressure, and can be introduced by blowing an inert gas such as nitrogen during the reaction.
In addition, when using a fatty acid, an acid catalyst such as sulfuric acid or p-toluenesulfonic acid is used. When using a fatty acid derivative, an alkali catalyst such as sodium methylate, caustic potash or caustic soda is used. The reaction can proceed efficiently in a short time.
In addition, when the resulting 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 dissolved in an organic solvent such as ethanol. It is preferable to make it liquid.

(C) A component can be used individually by 1 type or in mixture of 2 or more types.
(C) It is preferable that it is 0.1-10 mass% in content of a liquid detergent composition, and, as for content of a component, it is more preferable that it is 0.5-5 mass%.
When the content of the component (C) is 0.1% by mass or more, the effect of suppressing fuzz in the article to be washed is further improved. When the content of the component (C) is 10% by mass or less, a blending balance with the component (B) can be particularly obtained, and the effect of suppressing fuzzing is further improved.

  In the liquid detergent composition of the present invention, the mixing ratio [(B) / (C)] of the component (B) and the component (C) is (B) / (C) = 1/10 by mass ratio. It is preferable to be in the range of ˜1 / 1. When (B) / (C) is in the above range, the effect of suppressing fuzz in the article to be washed is further improved. In addition, when (B) / (C) is equal to or higher than the lower limit, the effect of suppressing fuzz in the article to be washed becomes better, and when it is equal to or lower than the upper limit, the viscosity of the liquid detergent composition increases excessively. Can be prevented, and handling becomes easy.

In the liquid cleaning composition of this invention, the effect which mainly suppresses the fluff in a to-be-washed | cleaned object is acquired by containing the said (B) component. Moreover, the effect which suppresses the fluff in a to-be-washed object synergistically improves by using combining the said (B) component and the said (C) component.
The reason why such an effect is obtained is not clear, but is presumed as follows.
As described above, “fluffing in an object to be washed” is caused by rubbing or entanglement between objects to be washed such as clothes during washing in washing.
In the liquid detergent composition of the present invention, by adding the component (B) to the component (A), the frictional force when the objects to be washed are rubbed or entangled in the washing liquid is reduced. Is considered to be suppressed. Furthermore, since the frictional force is further reduced by using the component (C), it is considered that fuzzing is further suppressed.

<Optional component>
In addition to the above components (A) to (C), other components can be appropriately blended in the liquid detergent composition of the present invention as necessary within a range not impairing the effects of the present invention.

(Surfactant)
In the liquid detergent composition of the present invention, a surfactant other than the above components (A) and (C) may be blended depending on the application, for example, an anionic surfactant, an amphoteric surfactant, a cationic interface. An activator or the like can be used.
As an anionic surfactant, polyoxyethylene alkyl sulfate ester salt, α-olefin sulfonate, alkylbenzene sulfonate, α-sulfo fatty acid salt, soap, phosphate ester surfactant, acyl alaninate, acyl Examples include taurate.
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Can be mentioned.
Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkylpyridinium salts.

(Organic solvent)
In the liquid detergent composition of the present invention, alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol; glycols such as propylene glycol, butylene glycol and hexylene glycol; diethylene glycol and triethylene glycol , Tetraethylene glycol, polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, polyglycols such as dipropylene glycol; water miscibility such as alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether The organic solvent can be used. The content of the organic solvent is preferably 0.1 to 15% by mass in the liquid detergent composition.

(silicone)
In the liquid detergent composition of the present invention, CF1188HV, SH3748, SH3749, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET manufactured by Toray Dow Corning Co., Ltd. L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN F SILET 009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009 05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22; Polyether modification such as X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd .; TSF4450, TSF4452 and TSF4445 (trade name) manufactured by GE Toshiba Silicone Silicone can be used. The content of the polyether-modified silicone is preferably 0.1 to 3% by mass in the liquid detergent composition.

Further, in the liquid detergent composition of the present invention, it is possible to use paratoluenesulfonic acid, benzoate (which also has an effect as a preservative), a thinning agent or solubilizer such as urea. The content of the thinning agent or solubilizing agent is preferably 0.01 to 30% by mass in the liquid detergent composition.
In the liquid detergent composition of the present invention, metal ion scavengers such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid and citric acid can be used. The content of the metal ion scavenger is preferably 0.1 to 20% by mass in the liquid detergent composition.
In the liquid detergent composition of the present invention, an antioxidant such as butylhydroxytoluene, dibutylhydroxytoluene (BHT), distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like can be used. The content of the antioxidant is preferably 0.01 to 2% by mass in the liquid detergent composition.
Further, in the liquid detergent composition of the present invention, a preservative such as an isothiazolone liquid (trade name Caisson CG manufactured by Rohm and House) or the like can be used. It is preferable that content of the said preservative is 0.001-1 mass% in a liquid detergent composition.

  Furthermore, in the liquid detergent composition of the present invention, an enzyme (protease, lipase, cellulase, etc.), texture improver, alkali builder such as alkanolamine, pH adjuster, Troping agents, fluorescent agents, dye transfer inhibitors, anti-staining agents, pearl agents, soil release agents, and the like can be used.

In addition, for the purpose of improving the added value of a product, a coloring agent, an emulsifying agent, a fragrance for aroma, and the like can be used.
Colorants include 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, and Turquoise P-GR (all trade names) Can be used. The content of the colorant is preferably 0.00005 to 0.005% by mass in the liquid detergent composition.
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, polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd., trade name: Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be used. The content of the emulsifying agent is preferably 0.01 to 0.5% by mass in the liquid detergent composition.
As a fragrance | flavor, the fragrance | flavor component as described in Unexamined-Japanese-Patent No. 2002-146399 is mentioned. It is preferable that content of the said fragrance | flavor is 0.01-2 mass% in a liquid detergent composition.

In the liquid detergent composition of the present invention, pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide and alkanolamine And ammonia, and sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable from the viewpoint of stability over time of the liquid detergent composition.
A pH adjuster can be used individually by 1 type or in mixture of 2 or more types.
The pH adjuster is appropriately added in an amount for adjusting the pH of the liquid detergent composition at 25 ° C., preferably to pH 3-8.

As for pH of the liquid detergent composition of this invention, it is preferable that pH in 25 degreeC is 3-8, and it is more preferable that it is pH 5-8. When the pH is 5 to 9, even when the liquid detergent composition is stored for a long period of time, a uniform appearance is ensured and stability over time can be kept good.
The adjustment of the pH can be controlled, for example, by adding a certain amount of sulfuric acid, sodium hydroxide or the like. In addition, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide or sodium hydroxide can be further added for fine adjustment of pH.
In the present invention, the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).

The viscosity of the liquid detergent composition of the present invention is preferably 300 mPa · s or less, more preferably 1 to 250 mPa · s at 25 ° C. If the said viscosity is 300 mPa * s or less, the discharge property from the container of a liquid detergent composition will become favorable, and will become easier to use.
In the present invention, the viscosity of the liquid detergent composition (temperature adjusted to 25 ° C.) is determined by placing the liquid detergent composition in a 300 ml beaker and using a BL type viscometer. A value measured under the conditions of 1 rotor, 60 rpm, and a rotation time of 60 seconds is shown.

The liquid detergent composition of the present invention can be produced based on a conventional method, preferably using water as a solvent.
The usage method is a normal usage method, that is, a method in which the liquid detergent composition of the present invention (product of the present invention) is poured into water together with the object to be washed at the time of washing. Examples thereof include a method of directly applying the product of the present invention, a method of preliminarily dissolving the product of the present invention in water and immersing the article to be washed. Also preferred is a method in which the product of the present invention is applied to the article to be washed, and then allowed to stand as appropriate, followed by ordinary washing using ordinary washing liquid.

As described above, according to the present invention, it is possible to provide a liquid detergent composition excellent in the effect of suppressing fuzz in an object to be washed.
The liquid detergent composition of the present invention can ensure a uniform appearance even when stored for a long period of time, and has good stability over time.
According to the liquid detergent composition of the present invention, it is possible to sufficiently suppress fuzz in an object to be washed without using cellulase or the like.
The liquid detergent composition of the present invention is particularly suitable for clothing.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

≪Manufacture of liquid detergent composition≫
According to the composition shown in Tables 1 to 3, the liquid detergent compositions of the respective examples were prepared by the methods shown below. The unit of the compounding amount in Tables 1 to 3 is mass%, and any component indicates a pure equivalent amount.
In addition, the liquid cleaning composition of each example was manufactured so that the sum total of each component as described in a table | surface might be 100 mass%. Each component used was kept at 50 ° C.
[Method for producing liquid detergent composition]
First, the component (A) was placed in a cylindrical glass bottle (diameter 50 mm, height 100 mm) containing a 2 cm stir bar. Next, the mixed solution of arbitrary components was put, and the stirring bar was stirred at 400 rpm.
Subsequently, in each example except the comparative example 1 and the comparative example 3, (B) component was put and stirred, and in Example 10-17 and the comparative example 3, (C) component was put in order and stirred and mixed continuously. . Thereafter, purified water is added so that the total amount (the total amount is 100 parts by mass) is 95 parts by mass, and after stirring and mixing, the pH is adjusted and the remaining amount is adjusted so that the total amount becomes 100% by mass. Of purified water was added to produce a liquid detergent composition.
The pH was adjusted by adding an appropriate amount of a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH of the liquid cleaning composition at 7.0 was 7.0.
The pH was measured by adjusting the liquid detergent composition to 25 ° C. and using a glass electrode type pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). The measuring method was performed based on JISK3362-1998.
Moreover, the viscosity at 25 degreeC of the liquid cleaning composition of each example was adjusted to 150 mPa * s. The viscosity was measured by placing the liquid detergent composition in a 300 ml beaker and using a BL type viscometer. The test was performed under the conditions of 1 rotor, 60 rpm, and a rotation time of 60 seconds.
Below, the component shown in the table | surface is demonstrated.

<Description of components shown in the table>.
-Component (A) SLAO: Safol 23 alcohol (trade name, manufactured by Sasol) ethylene oxide with an average addition mole number of 15 mole adducts (those having an alkyl group having 12 carbon atoms and those having an alkyl group having 13 carbon atoms) Mixture of 6/4 in mass ratio (C12 / C13), branching ratio: 50 mol%).
In the present specification, “branch ratio” indicates the ratio of the number of moles of alcohol having a branched alkyl group to the number of moles of the whole alcohol in the raw material alcohol.
[Synthesis Method of SLAO]
224.4 g of Safol 23 alcohol manufactured by Sasol and 2.0 g of 30% by mass NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Thereafter, while stirring the alcohol, 763.4 g of ethylene oxide (gaseous) was gradually added into the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C., using a blowing tube. .
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, to obtain SLAO.

SLAL: Safol 23 alcohol (trade name, manufactured by Sasol), an ethylene oxide average addition mole number of 12 mole adduct (mass ratio of C12 alkyl group and C13 alkyl group) (C12 / C13) 6/4 mixture, branching ratio: 50 mol%).
[Synthesis method of SLAL]
In the above [Synthesis Method of SLAO], SLAL was obtained in the same manner as in [Synthesis Method of SLAO] except that 224.4 g of Safol 23 alcohol manufactured by Sasol and 610.7 g of ethylene oxide (gaseous) were used.

  TO7: Lutenzol TO7 (trade name, manufactured by BASF), an average addition mole number of ethylene oxide of 7 moles (those having an alkyl group having 13 carbon atoms, branching rate: 100 mole%).

-Component (B) MLP: Leogard MLP (manufactured by Lion Corporation), degree of cationization: 0.6 mass%, weight average molecular weight: 1.6 million.

LF: Cationized cellulose LF synthesized by the following synthesis method.
[Synthesis Method of Cationized Cellulose LF]
Hydroxyethyl cellulose (manufactured by Sumitomo Seika, trade name: LF-15, 1% by weight aqueous solution viscosity (25 ° C.): 700 to 1300 mPa · s) 30 g (100 parts by mass), isopropyl alcohol / water (mass ratio) = 85 / Then, 300 g (1000 parts by mass) of a mixed solvent to be 15 and 4.5 g (15 parts by mass) of a 25% by mass aqueous sodium hydroxide solution were added and mixed. Next, the mixture was stirred and mixed for 30 minutes, and 150 g (500 parts by mass) of the supernatant of the mixed solvent was extracted.
Thereafter, the temperature was raised to 50 ° C., and 4 g (13 parts by mass) of glycidyltrimethylammonium chloride (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, effective concentration: 73% by mass aqueous solution) was added as a cationizing agent for 3 hours. Reacted. Thereafter, a 10% by mass isopropyl alcohol hydrochloride solution was added to adjust the pH to 6 to obtain a cationized cellulose slurry.
And it spin-dehydrated and passed through drying (70-80 degreeC), and obtained cationized cellulose LF (weight average molecular weight: 900,000, cationization degree: 0.6 mass%).

MGP: Leogard MGP (trade name, manufactured by Lion Corporation), degree of cationization: 0.4 mass%, weight average molecular weight: 1.3 million.
KGP: Leogard KGP (trade name, manufactured by Lion Corporation), degree of cationization: 1.3% by mass, weight average molecular weight: 120,000.
Cationized guar gum: Labor gum CG-M (trade name, manufactured by Dainippon Pharmaceutical Co., Ltd.), degree of cationization: 1.2% by mass, weight average molecular weight: 250,000.

Component (C) C10 Amidoamine: Amidopropyldimethylamine caprate (synthetic product).
[Method for synthesizing C10 amidoamine]
A 1-liter four-necked flask equipped with a reflux condenser was charged with 260.9 g of methyl caprate (manufactured by Lion Chemical Co., Ltd., trade name: Pastel M-10, molecular weight 186), and nitrogen substitution was performed twice at 60 ° C. Thereafter, the temperature was raised to 150 ° C., and 186 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to the mixed fatty acid: 1.30) was added dropwise over 1.5 hours. After completion of dropping, the mixture was kept at 185 to 190 ° C. and aged for 7 hours to obtain C10 amidoamine. The conversion rate of the mixed fatty acid calculated from the acid value was 97.2%.

C16 / 18 amidoamine: long chain fatty acid amidopropyldimethylamine (mass ratio of stearic acid / palmitic acid = 7/3) (synthetic product).
[Method for synthesizing C16 / 18 amidoamine]
A 1-liter four-necked flask equipped with a reflux condenser was charged with 252 g of stearic acid (molecular weight 284) and 108 g of palmitic acid (molecular weight 256), and heated to 80 ° C. to melt the stearic acid. After carrying out nitrogen substitution twice, the temperature was raised to 150 ° C., and 127 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to the mixed fatty acid: 0.95) was added dropwise over 1 hour. Next, after maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 47 g of dimethylaminopropylamine was further added dropwise over 1 hour. After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, the pressure was reduced (4.0 kPa) while maintaining the temperature at 170 to 190 ° C., and the mixture was allowed to stand for 1 hour, whereby unreacted dimethylaminopropylamine was distilled off to obtain C16 / 18 amidoamine. The conversion rate of the mixed fatty acid calculated from the acid value was 99.2%.

C18 amidoamine: amidopropyldimethylamine stearate (synthetic product).
[Method for synthesizing C18 amidoamine]
A 1 liter four-necked flask equipped with a reflux condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour. Next, after hold | maintaining at 150-160 degreeC for 1 hour, it heated up at 185 degreeC over 1 hour, and also 45 g of dimethylaminopropylamine was dripped over 1 hour. After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, the pressure was reduced (4.0 kPa) while maintaining at 170 to 190 ° C., and the mixture was left for 1 hour to distill off unreacted dimethylaminopropylamine to obtain C18 amidoamine. The conversion rate of stearic acid calculated from the acid value was 99.6%.

-Optional component Sodium benzoate: Sodium benzoate (trade name, manufactured by Toa Gosei Co., Ltd.).
Trisodium citrate: sodium citrate (trade name, manufactured by Miles (USA)).
Paratoluenesulfonic acid: PTS acid (trade name, manufactured by Kyowa Hakko Kogyo Co., Ltd.).
Dibutylhydroxytoluene: SUMILZER BHT-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
Isothiazolone liquid: Caisson CG (trade name, 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture; Rohm and House Made).
Dye (Acid Red 138): Suminol Milling Brilliant Red BS (trade name, manufactured by Sumitomo Chemical Co., Ltd.)
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd., pH adjuster.
Sulfuric acid: Toho Zinc Co., Ltd. pH adjuster.
water.

The “common component a” used in the liquid cleaning composition of each example is shown below.
Common component a:
Sodium benzoate 0.5% by mass
Trisodium citrate 0.2% by mass
Paratoluenesulfonic acid 2.0% by mass
Dibutylhydroxytoluene 0.03% by mass
Fragrance 0.2% by mass
Isothiazolone solution 0.01% by mass
Dye (Acid Red 138) 0.0003 mass%
pH adjuster appropriate amount water balance

≪Evaluation method≫
About the obtained liquid cleaning composition, the suppression effect of the fluff in a to-be-washed object was evaluated by the method and evaluation criteria shown below, and the result was written together in Tables 1-3.

<Evaluation of the suppression effect of fuzz in the washing object>
A commercially available T-shirt (manufactured by Plus One International Co., Ltd.) was used as the evaluation fabric.
The pretreatment shown below was applied to the evaluation fabric.
[Preprocessing]
A 50-degree C tap water was used in a two-tank washing machine (product name: CW-C30A1-H type ₁ , manufactured by Mitsubishi Electric Corporation), and Akron (trade name, manufactured by Lion Corporation) was used at a standard concentration (water supply The bathing ratio is 30 times in 30 mL of water (30 mL of water) and the evaluation cloth is washed for 15 minutes and then dehydrated for 5 minutes. After washing and dewatering operations are repeated twice, the running water is rinsed for 15 minutes and then dehydrated for 5 minutes. The rinsing / dehydrating operation was repeated 5 times, and then hung at room temperature.

[Cleaning treatment]
Using a fully automatic electric washing machine (product name: JW-Z23A) manufactured by Haier as a washing machine, washing the evaluation cloth subjected to the above pretreatment with tap water with a bath ratio of 30 times and a water temperature of 20 ° C. did.
In this cleaning process, the liquid cleaning composition of each example was added to the cleaning solution so as to have a use concentration of 1333 ppm, and the cleaning process was performed. This washing process was repeated three times, and the evaluation cloth hung and dried at room temperature was used for the evaluation of the fuzz suppression effect.

[Evaluation of fuzz suppression effect]
Based on the following score, a paired comparison was performed by 10 professional panelists.
In the evaluation of the paired comparison, as a control, an evaluation cloth that was not subjected to the cleaning treatment and was subjected only to the pretreatment was used.
Score:
+2: Compared to the control.
+1: Slightly better than the control.
0: Equivalent to control.
-1: Slightly worse than the control.
-2: It is worse than the control.
As a result of the evaluation of the pair comparison, when the total score of 10 people is 16-20 points, ◎◎, when 11-15 points, ◎, when 6-10 points, △, when 1-5 points, △, The case where the score was 0 or less was evaluated as x.
In this evaluation, if it was more than (triangle | delta), it shall have the effect which suppresses fluff.

As is clear from the above results, the liquid detergent compositions of Examples 1 to 17 according to the present invention have the effect of suppressing fuzz in the object to be washed as compared with the liquid detergent compositions of Comparative Examples 1 to 3. It was confirmed that it was excellent.
From the comparison of Examples 2, 4 to 7, and 10 to 14, the liquid detergent composition of Examples 10 to 14 that further contains the component (C) has a more excellent effect of suppressing fuzz in the article to be cleaned. It could be confirmed.

  On the other hand, the liquid detergent compositions of Comparative Example 2 in which the content ratio of the component (B) is less than 0.1% by mass and Comparative Examples 1 and 3 lacking the component (B) are all fluffy in the object to be cleaned. It was confirmed that the inhibitory effect was low.

Claims (3)

  A nonionic surfactant (A) and at least one cationic polymer compound (B) selected from the group consisting of cationized cellulose and cationized guar gum are contained in an amount of 0.1 to 5% by mass. Liquid detergent composition.   A tertiary amine having a hydrocarbon group having 7 to 28 carbon atoms (however, the hydrocarbon group may have a substituent and may have a linking group in the chain) and / or The liquid detergent composition according to claim 1, further comprising a nitrogen-containing compound (C) which is a salt thereof.   The mixing ratio [(B) / (C)] of the cationic polymer compound (B) and the nitrogen-containing compound (C) is in a range of 1/10 to 1/1 by mass ratio. The liquid detergent composition as described.