JP2010189612A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition excellent in the soil redeposition effect of washed things, also excellent in appearance stability without getting cloudy, and capable of preventing the washing vessel from being dented as a result of that oxygen in the washing vessel is absorbed. <P>SOLUTION: The liquid detergent composition includes (A) a specific alkylene oxide adduct, (B) a straight-chain alkylbenzenesulfonic acid, (C) an alkanolamine, and (D) hydrogen peroxide, wherein the component (A) accounts for 50-70 mass% of the whole detergent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

The liquid detergent composition has characteristics that are different from powdered detergents, such as being undissolved during use and enjoying a fragrance. The liquid detergent composition is also rapidly increasing in demand due to its reasonable price. Conventionally, the liquid detergent composition has to be contained in a container in a certain amount in order to satisfy a certain period of use. Therefore, there is a problem that the product is heavy when it is held by hand, and it is difficult to take it home from the store, and attempts have been made to minimize the amount of the liquid detergent composition contained in the container.
In addition, in order to reduce the burden on the environment, attempts have been made to reduce the amount of liquid detergent composition used, or to reduce the size of the container in which the liquid detergent composition is stored to reduce garbage. Yes. As a liquid detergent composition that solves the above-mentioned problems, a liquid detergent composition having a high surfactant concentration, which is called “concentrated type”, has been developed.

However, the viscosity of a general-purpose nonionic surfactant such as polyoxyethylene alkyl ether used as a cleaning component of the liquid cleaning composition increases remarkably as the concentration increases. Therefore, gelation is likely to occur when the liquid detergent composition having a high concentration of the nonionic surfactant is used. In such general-purpose nonionic surfactants, the concentration at which gelation occurs is relatively low, and it is difficult to produce a liquid detergent composition containing 50% by mass or more of the nonionic surfactant.
In particular, in a liquid detergent composition containing a high concentration nonionic surfactant, the usability is likely to deteriorate due to gelation of the liquid detergent composition itself on the liquid surface over time. When the liquid detergent composition is gelled, the metering property when the liquid detergent composition is measured on the cap, the deterioration of the dischargeability and solubility of the liquid detergent composition into the washing machine at the inlet of the washing machine, etc. Occurs.
Therefore, a liquid detergent composition in which a nonionic surfactant is a specific polyoxyethylene fatty acid methyl ester is shown as a liquid detergent composition that hardly gels even after long-term storage and has excellent liquid stability. (Patent Documents 1 and 2).

In recent years, the drums of drum-type washing machines have been extended with the increase in the size of washing machines, and many clothes have been packed, so the amount of washing water for the laundry has decreased, so-called low bath ratio has occurred. ing. In such a laundry environment, even if the dirt is detached from the clothes, the dirt easily adheres to the same clothes or the dirt moves to another clothes, so that the laundry is easily recontaminated. Softeners are another cause for these problems. It has been found that when a softener is overused in a low-bath washing environment such as a drum-type washing machine, the cationic surfactant, which is a soft base material, tends to remain on the clothing along with dirt, and re-contamination tends to occur I came.
As a method for suppressing the re-contamination of laundry, it is effective to remove the cationic surfactant present together with the soil, and the addition of an anionic surfactant in addition to the nonionic surfactant is effective as a composition. is there. However, when an anionic surfactant is blended under a liquid detergent composition containing a high concentration of nonionic surfactant, white turbidity may occur and appearance stability may be reduced. Therefore, in order to improve the appearance stability of the liquid detergent composition combined with the anionic surfactant, it is considered to use alkanolamine as a counter ion of the anionic surfactant. However, when alkanolamine is used, the alkanolamine absorbs oxygen in the headspace of the container in the presence of the nonionic surfactant, causing a problem that the container is recessed and the appearance of the product is impaired. In particular, when the nonionic surfactant that is the main base material is at a high concentration, the oxygen absorption amount is remarkably increased. Therefore, it is very important to suppress the oxygen absorption in order to use alkanolamine.

  On the other hand, even when alkanolamine is not used, the container may be recessed when the nonionic surfactant is stored for a long period of time. About this problem, the method of suppressing the dent of a container using a radical scavenger and a metal ion scavenger is shown (patent document 3).

JP 2008-7706 A JP 2008-7707 A JP 2007-308598 A

  Then, like patent document 3, it is possible to suppress oxygen absorption by alkanolamine by containing a radical scavenger and a metal ion scavenger. As a result of examining the method, the liquid detergent composition containing a high concentration of nonionic surfactant, anionic surfactant, and alkanolamine has a very large amount of oxygen absorbed by the alkanolamine, and the radical scavenger and the metal ion The scavenger could not sufficiently inhibit oxygen absorption.

  The present invention is a liquid detergent composition excellent in the effect of preventing recontamination of laundry, a liquid that does not cause white turbidity in the composition, is excellent in appearance stability, and can suppress the depression of the container An object is to provide a cleaning composition.

The present invention employs the following configuration in order to solve the above problems.
[1] Component (A): alkylene oxide adduct represented by the following formula (I), (B) component: linear alkylbenzene sulfonic acid, (C) component: alkanolamine, (D) component: excess A liquid detergent composition comprising hydrogen oxide, wherein the content of the component (A) is 50 to 70% by mass.

(However, R ¹ is a linear or branched alkyl group having 9 to 13 carbon atoms, or a linear or branched alkenyl group having 9 to 13 carbon atoms, and R ² is 2 to 2 carbon atoms. 4 is an alkylene group, R ³ is an alkyl group having 1 to ³ carbon atoms, and n is an integer of 5 to 30.)
[2] The liquid detergent composition according to [1], further comprising (E) component: a metal ion scavenger.
[3] The liquid cleaning composition according to [1] or [2], further comprising (F) component: a phenol radical scavenger.

  Conventionally, hydrogen peroxide is widely used in liquid detergent compositions whose main purpose is bleaching. On the other hand, the present invention solves the problem that a container is dented due to rapid oxygen absorption by alkanolamine in a liquid detergent composition containing a high concentration of nonionic surfactant. The present inventors have found a new effect of suppressing the dent of the container by suppressing it, and have completed the invention.

  The liquid detergent composition of the present invention is excellent in the effect of preventing re-contamination of laundry, and also has excellent appearance stability without causing white turbidity, etc. It is suppressed.

  The liquid detergent composition of the present invention (hereinafter referred to as “the present composition”) includes an alkylene oxide adduct represented by the above formula (I) as the component (A) and a linear chain as the component (B). It is a composition containing alkylbenzene sulfonic acid, (C) component alkanolamine, and (D) component hydrogen peroxide.

((A) component)
The component (A) is an alkylene oxide adduct represented by the following formula (I) and plays a role as a nonionic surfactant. By using the component (A), the present composition can ensure good liquid stability that does not cause gelation even if it contains a high concentration of nonionic surfactant. Moreover, since this composition is excellent in the solubility to water by containing (A) component, high detergency is acquired. Furthermore, even if the concentration of the component (A) is high, the viscosity is suppressed from increasing significantly, and the fluidity is also good.

R ¹ in the component (A) is a linear or branched alkyl group, or a linear or branched alkenyl group having a carbon number of 9 to 13 9 to 13 carbon atoms.
In R ¹ , the alkyl group and the alkenyl group preferably have 10 to 13 carbon atoms, and more preferably 11 to 13 carbon atoms, from the viewpoint of improving detergency and preventing gelation.

R ² is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In the component (A), R ² may be a single alkylene group or a mixture of two or more alkylene groups.

R ³ is an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.
n shows the average addition mole number of alkylene oxide, and is 5-30. n is preferably 12 to 18 from the viewpoint of improvement in detergency and liquid stability of the composition (particularly stability over time at a low temperature). The average number of moles added means the average number of moles of alkylene oxide added per mole of fatty acid alkyl ester.
(A) A component may be used individually by 1 type and may use 2 or more types together.

In the component (A), the narrow ratio W represented by the following formula (1) is preferably 20% by mass or more, and the upper limit is substantially preferably 80% by mass or less. The narrow ratio W means the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide. The narrow ratio W is more preferably 20 to 60% by mass, and more preferably 30 to 45% by mass from the viewpoint that the temporal stability of the composition at low temperature is particularly excellent.
The higher the narrow rate of the present composition, the better the detergency. When the narrow ratio is 20% by mass or more, particularly 30% by mass or more, the present composition with less raw material odor of the component (A) which is a nonionic surfactant is easily obtained. This is because, after the production of the component (A), the fatty acid ester which is the raw material of the component (A) coexisting with the component (A), and the alkylene oxide adduct of n = 1 and n = 2 in the above formula (I) This is considered to be because the amount of the amount decreases.

N _max in the above formula (1) represents the number of moles of alkylene oxide added in the alkylene oxide adduct most present in all alkylene oxide adducts. i represents the number of added moles of alkylene oxide. Yi represents the proportion (% by mass) of the alkylene oxide adduct present in all alkylene oxide adducts, where the number of moles of alkylene oxide added is i.
The narrow rate W can be controlled, for example, by adjusting the catalyst in the production method described later.

  The method for producing the component (A) is not particularly limited. For example, a method in which an alkylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP 2000-144179 A). Can be manufactured more easily.

As the surface-modified composite metal oxide catalyst, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) were added to magnesium oxide or the like. A catalyst in which a composite metal oxide is surface-modified with a surface modifier such as metal hydroxide and / or metal alkoxide, and hydrotalcite that is a composite metal oxide is surface-modified with the surface modifier, A calcined catalyst is preferred.

In the surface modification of the composite metal oxide catalyst, the amount of the surface modifier used relative to 100 parts by weight of the composite metal oxide is preferably 0.5 to 10 parts by weight, and 1 to 5 parts by weight. It is more preferable. If the amount used is 0.5 parts by mass or more, the modification effect is easily obtained. Moreover, if the said usage-amount is 10 mass parts or less, sufficient catalyst activity will be easy to be obtained.
Further, by controlling the amount of the surface modifier used for the surface modification in the composite metal oxide catalyst, the narrow ratio W of the component (A) produced by the composite metal oxide catalyst can be controlled. As the amount of the surface modifier used increases, the component (A) having a higher narrow rate W can be obtained.

  Content of (A) component in this composition (100 mass%) is 50-70 mass%, It is preferable that it is 51-65 mass%, and it is more preferable that it is 55-60 mass%. When the content of the component (A) is 50% by mass or more, good detergency can be obtained. Moreover, since the usage-amount of this composition per time can be reduced and a container can also be made small, garbage can be reduced and an environmental load can be reduced. Therefore, the effectiveness (commercial value) as a concentrated liquid cleaning composition is increased. When the content of the component (A) is 70% by mass or less, gelation or the like on the liquid surface with the passage of time in the composition is difficult to occur, and a film is hardly formed on the liquid surface.

In the molecular structure of the component (A) in the present invention, a hydrophilic group does not exist at the end of the molecule (end-capped type), and the molecule has a highly polar carbonyl group. Thereby, (A) component becomes a nonionic surfactant with which the orientation of a molecule | numerator is weak in aqueous solution, and a micelle is unstable. Therefore, it is considered that even when the concentration of the component (A) is high, gelation or the like is suppressed, and the present composition in which the concentration of the component (A) is 50% by mass or more can be obtained while maintaining good liquid stability.
Moreover, it is estimated that this composition improves the solubility to water by using (A) component as a nonionic surfactant. Furthermore, it is considered that the component (A) contributes to good fluidity at a high concentration. Therefore, after the (A) component is put into the water in the washing machine tub, the concentration of the (A) component is quickly uniform in the washing liquid, and since it comes into contact with the article to be washed at a predetermined concentration from the initial stage of washing, it is high. It is thought that the cleaning power is demonstrated.

((B) component)
The component (B) is a linear alkylbenzene sulfonic acid (LAS-H). That is, the component (B) is an anionic surfactant, and when used in combination with the component (A), a recontamination preventing effect can be obtained.
The number of carbon atoms in the alkyl group of the linear alkylbenzene sulfonic acid is preferably 8 to 16, and more preferably 10 to 14.

  The content of the component (B) in the present composition (100% by mass) is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass. If content of (B) component is 0.1 mass% or more, the recontamination prevention effect will be easy to be exhibited. In addition, if the content of the component (B) is 10% by mass or less, the amount of the later-described component (C) which is a counter ion of the component (B) can be reduced accordingly, so that the oxygen of the component (C) It is easy to suppress the container from being dented by absorption.

((C) component)
Component (C) is an alkanolamine. Component (C) is a counter ion of component (B), and when the components (A) and (B) are used in combination, the composition is prevented from becoming clouded and the appearance stability of the composition is improved. Play a role to improve.
The alkanolamine is not particularly limited as long as it functions as a counter ion for the component (B), and is preferably an alkanolamine having an alkyl group having 1 to 3 carbon atoms, and an alkanolamine having an alkyl group having 1 to 2 carbon atoms. More preferably, monoethanolamine, diethanolamine, and triethanolamine are more preferable.
(C) A component may be used individually by 1 type and may use 2 or more types together.

  The content of the component (C) in the composition (100% by mass) is preferably 0.1 to 3% by mass, more preferably 0.5 to 3% by mass, More preferably, it is 2 mass%. If content of (C) component is 0.1 mass% or more, the effect of improving the external appearance stability of this composition will be easy to be acquired. Moreover, if content of (C) component is 3 mass% or less, it will be easy to suppress that a container dents by the oxygen absorption of (C) component.

((D) component)
Component (D) is hydrogen peroxide. (D) component plays a role which suppresses that a (C) component absorbs oxygen and a container dents in this composition. Hydrogen peroxide may be used for the purpose of obtaining a bleaching effect in a conventional liquid detergent composition. In the present invention, the present invention and others conducted various studies on the suppression of the dent in the container due to the absorption of oxygen of the component (C), and found that hydrogen peroxide has the suppression effect. It was unexpected that it had such an effect. The reason why oxygen absorption of the alkanolamine (C) can be suppressed by containing hydrogen peroxide is that oxygen absorption involves oxidation of nonionic surfactant, alkanolamine and oxygen by generating radicals as intermediates. Although it is presumed that a product is formed, it is thought that this is because the component (D) traps radicals on the way.

  In addition, the component (D) in the present invention is contained for the purpose of suppressing dents in the container due to oxygen absorption of the component (C) as described above, but the composition also has bleaching performance due to the component (D). Has been granted. Moreover, the effect which the recontamination prevention effect improves is also acquired by containing (D) component. The reason for this is considered that the component (D) makes it difficult for the laundry to be recontaminated by denaturing the protein soil out of the soil in the washing liquid.

  The content of the component (D) in the composition (100% by mass) is preferably 0.1 to 10% by mass, more preferably 0.5 to 6% by mass, and 1 to 6% by mass. % Is more preferable. If content of (D) component is 0.1 mass% or more, the effect which suppresses that a container will dent by the oxygen absorption of (C) component will be easy to be acquired. Moreover, if content of (D) component is 10 mass% or less, the balance with another component will become favorable.

((E) component)
In addition to the component (A), the component (B), the component (C) and the component (D), the composition contains a metal ion scavenger as the component (E) as necessary. Also good. The metal ion scavenger of component (E) has an effect of capturing polyvalent metal ions such as calcium, magnesium, iron and the like. Examples of the metal ion scavenger include the compounds shown below.
Compound (E1): Aminopolyacetic acid or a salt thereof.
Compound (E2): Organic acid or salt thereof.
Compound (E3): an amino acid or a salt thereof.
Compound (E4): polycarboxylic acid polymer or salt thereof.
Compound (E5): Organic phosphonic acid or a salt thereof.

Examples of the compound (E1) include aminopolyacetic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and salts thereof.
Examples of the compound (E2) include organic acids such as lactic acid, malonic acid, succinic acid, tartaric acid, oxalic acid, malic acid, diglycolic acid, and citric acid or salts thereof.
Examples of the compound (E3) include amino acids such as aspartic acid, glutamic acid and glycine or salts thereof.
As the compound (E4), for example, a polycarboxylic acid polymer having a mass average molecular weight of 3000 to 100,000 or a salt thereof obtained by polymerizing one or more monomers such as acrylic acid, methacrylic acid, and maleic anhydride. Can be mentioned.
Examples of the compound (E5) include organic phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid or salts thereof.
(E) A component may be used individually by 1 type and may use 2 or more types together.
Component (E) is preferably compound (E2) or compound (E5) from the viewpoint of the effect of suppressing oxygen absorption by component (C) and the liquid stability of the composition.

  The content of the component (E) in the composition (100% by mass) is preferably 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, More preferably, it is 0.5 mass%.

Moreover, in this composition, in order to acquire the further oxygen absorption inhibitory effect, the phenol type radical scavenger which is (F) component may contain. The phenol radical scavenger is one or more compounds selected from the group consisting of phenol and phenol derivatives, and is a compound having a function of scavenging radicals. Examples of the phenol derivative include the following compounds.
Compound (F1): A compound having a substituent derived from a phenolic hydroxyl group.
Compound (F2): A compound having a phenolic hydroxyl group.
However, the compound (F1) is a compound having no phenolic hydroxyl group.

The substituent derived from the phenolic hydroxyl group in the compound (F1) means a group formed by substituting the hydrogen atom of the phenolic hydroxyl group with another substituent. Examples of the other substituents include aromatic groups (aryl groups) such as alkyl groups having 1 to 4 carbon atoms and phenyl groups.
Examples of the compound (F1) include phenyl diglycol.

As the compound (F2), for example, a compound in which two or more hydrogen atoms in the benzene ring are substituted with a hydroxyl group (hereinafter referred to as “compound (F21)”), or one or more hydrogen atoms in the benzene ring are substituted with a hydroxyl group. And a compound in which one or more hydrogen atoms of the benzene ring are substituted with a substituent other than a hydroxyl group (hereinafter referred to as “compound (F22)”). Examples of the substituent other than the hydroxyl group in the compound (F22) include the other substituents and the alkyl group in the compound (F1).
Examples of the compound (F21) include catechol and hydroquinone.
Examples of the compound (F22) include methoxyphenol, dimethoxyphenol, and dibutylhydroxytoluene (BHT).

The component (F) is preferably the compound (F2), more preferably methoxyphenol, and particularly preferably 4-methoxyphenol from the viewpoint of the excellent effect of suppressing the oxygen absorption of the component (C).
(F) A component may be used individually by 1 type and may use 2 or more types together.

(Other optional ingredients)
Moreover, this composition may contain the following arbitrary components further as needed.
From the viewpoint of prevention of film formation, a glycol solvent may be contained.
Examples of the glycol solvent include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polyalkylene glycol butyl ether, and polyalkylene glycol phenyl ether. A glycol solvent may be used individually by 1 type, and may use 2 or more types together.
The content of the glycol solvent in the present composition (100% by mass) is preferably 0 to 20% by mass, and more preferably 1 to 10% by mass.

Moreover, the hydrotrope agent may be contained from the point of the liquid stability in low temperature.
Examples of the hydrotrope include sodium paratoluenesulfonate, sodium cumenesulfonate, and ethanol. A hydrotrope agent may be used individually by 1 type, and may use 2 or more types together.
The content of the hydrotrope in the present composition (100% by mass) is preferably 0 to 20% by mass, and more preferably 1 to 10% by mass.

Moreover, the saturated fatty acid may be contained mainly from the point which reduces foaming at the time of use of this composition. The saturated fatty acid may be linear or branched, and preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms.
Specific examples of the saturated fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Of these, palmitic acid is preferred because of its excellent foam reduction effect. Saturated fatty acid may be used individually by 1 type, and may use 2 or more types together.
The content of the saturated fatty acid in the composition (100% by mass) is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and 0.2 to 1% by mass. % Is more preferable. When the content of the saturated fatty acid is 0.05% by mass or more, an effect of reducing foaming is easily obtained. When the content of the saturated fatty acid is 3% by mass or less, precipitation or separation hardly occurs in the present composition, and the liquid stability becomes better.

Moreover, the recontamination prevention agent may be contained from the point of the improvement of the recontamination prevention effect.
Examples of the recontamination preventing agent include polyvinyl pyrrolidone, carboxymethyl cellulose, and soil release polymer. The recontamination inhibitor may be used alone or in combination of two or more.
The content of the anti-staining agent in the composition (100% by mass) is preferably 0 to 2% by mass.

Moreover, the enzyme may contain from the point which improves the detergency other than sebum dirt.
Examples of the enzyme include lipase, amylase, and cellulase.
It is preferable that content of the enzyme in this composition (100 mass%) is 0-1 mass%.

In addition, when an enzyme is used, an enzyme stabilizer such as boric acid, borax, formic acid or a salt thereof, calcium salts such as calcium chloride, calcium carbonate, and calcium sulfate may be contained in order to stabilize the enzyme. Good.
It is preferable that content of the enzyme stabilizer in this composition (100 mass%) is 0-3 mass%.

Moreover, you may contain silicone from the point of a texture improvement.
Examples of silicone include dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
It is preferable that content of the silicone in this composition (100 mass%) is 0-5 mass%.

Moreover, the fluorescent agent may contain from the point of the whiteness improvement of white clothing.
Examples of the fluorescent agent include a distyryl biphenyl type fluorescent agent.
It is preferable that content of the fluorescent agent in this composition (100 mass%) is 0-1 mass%.

Moreover, the pigment | dye may be contained in order to color this composition.
Examples of the pigment include acid dyes.
It is preferable that content of the pigment | dye in this composition (100 mass%) is 0.00001-0.001 mass%.

Moreover, the fragrance | flavor may contain for the purpose of fragrance.
As a fragrance | flavor, the fragrance | flavor composition containing the fragrance | flavor component, a solvent, and a stabilizer of Unexamined-Japanese-Patent No. 2002-146399 is mentioned, for example.
It is preferable that content of the fragrance | flavor in this composition (100 mass%) is 0.01-1 mass%.

(This composition)
This composition is suitable for components (A), (B), (C) and (D) as described above, together with optional components that can be blended as necessary, such as purified water such as ion-exchanged water, etc. It can manufacture by melt | dissolving in an appropriate solvent and adjusting content of these each component. This composition can be manufactured based on a conventional method.
The solid content concentration of the composition is preferably 10 to 60% by mass.

The pH of the present composition is preferably 5.0 to 8.0, more preferably 6.0 to 8.0. If pH is 5.0 or more, it will be easy to suppress that the (A) component which is a main base material is hydrolyzed, and storage stability will fall, and it will become difficult to reduce washing | cleaning performance. Moreover, if pH is 8.0 or less, (A) component will not be hydrolyzed easily and generation | occurrence | production of the gas by decomposition | disassembly of (D) component itself will not occur easily.
The pH can be adjusted by adding an alkanolamine as component (C) and then using an inorganic acid such as sulfuric acid or an inorganic base such as potassium hydroxide or sodium hydroxide as a pH adjuster.

The composition described above is excellent in detergency because it contains the alkylene oxide adduct of the component (A) at a high concentration of 50% by mass or more, and the amount used is a conventional liquid detergent composition. Compared to the amount used, it can be reduced to substantially half or less, and the environmental load can be reduced. Moreover, since the linear alkylbenzene sulfonic acid of (B) component is used together, it is excellent also in the effect of preventing recontamination. Moreover, since the alkanolamine of (C) component is contained as a counter ion of (B) component, this composition does not produce cloudiness etc. and is excellent in external appearance stability.
Furthermore, since this composition contains hydrogen peroxide as the component (D), it is suppressed that the container is depressed due to the rapid oxygen absorption of the component (C) in the presence of the component (A). Yes.
As described above, the composition has a high detergency and also has a re-contamination preventing effect, appearance stability, and a container dent suppressing effect associated with oxygen absorption. It can be suitably used as a so-called “concentrated type” liquid detergent composition having a high concentration.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description. In this example, “%” means “mass%” unless otherwise specified.
<Preparation of liquid detergent composition>
Each component used for the preparation of the liquid detergent composition is as follows.
[(A) component]
A-1: C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ (Synthetic product, narrow ratio W: 33%)
Compound A-1 was produced by a method based on the method described in JP-A No. 2002-144179. That is, alumina hydroxide / magnesium hydroxide (trade name: KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O is obtained at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina hydroxide / magnesium catalyst (unmodified) (2.2 g) obtained by calcining, 2.9 ml of 0.5N potassium hydroxide ethanol solution as a surface modifier, and 350 g of lauric acid methyl ester A 4-liter autoclave was charged and the catalyst was reformed in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 × 10 ⁵ Pa, 1079 g of ethylene oxide was introduced and reacted while stirring.
Subsequently, the reaction liquid was cooled to 80 ° C., and after adding 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids, the catalyst was filtered to obtain Compound A-1.

A-2: a mixture of C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ and C ₁₃ H ₂₇ CO (OC ₂ H ₄ ) ₁₅ OCH _{3 in} a mass ratio of 8: 2 (synthetic product, narrow ratio W: 33) %)
Compound A-2 was synthesized in the same manner as Compound A-1, except that instead of 350 g of lauric acid methyl ester, a mixture of 280 g of lauric acid methyl ester and 70 g of myristic acid was used, and 1052 g of ethylene oxide was introduced. Manufactured with.

[Component (B)]
B-1: Rypon LH-200 (trade name, linear alkylbenzene sulfonic acid (LAS-H), carbon number 10-14, average molecular weight 322, pure content 96%, manufactured by Lion Corporation)

[Component (C)]
C-1: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
C-2: Diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
C-3: Triethanolamine (manufactured by Nippon Shokubai Co., Ltd.)

[(D) component]
D-1: 35% aqueous solution of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Company)

[(E) component]
E-1: BRIQUEST ADPA-A (trade name, 1-hydroxyethane-1,1-diphosphonic acid, manufactured by Rhodia)
E-2: Liquid citric acid (trade name, citric acid, manufactured by Yushi Co., Ltd.)

[(F) component]
F22-1: MQ-F (trade name, 4-methoxyphenol, manufactured by Kawaguchi Chemical Co., Ltd.)
F22-2: Dibutylhydroxytoluene (BHT, manufactured by Degussa)

[Other optional ingredients]
Ethanol: 95 vol% synthetic ethanol (trade name, manufactured by NEDO)
PEG: PEG # 1000-L60 (trade name, polyethylene glycol, manufactured by Lion Corporation)
PHS-H: p-toluenesulfonic acid (manufactured by Kyowa Hakko)
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399

[Preparation method]
A liquid detergent composition having the composition shown in Table 1 was prepared as follows according to a conventional method.
In a cylindrical glass bottle (diameter 50 mm, height 100 mm) containing a 2 cm stirrer, put the components (A) and (B), then add the component (C) and optional components, and stir at 400 rpm. The mixture was stirred, and component (D) was further added and mixed with stirring. Thereafter, purified water is added so that the total amount becomes 90 parts by mass, and after stirring and mixing, the pH is adjusted, and further purified water is added so that the total amount becomes 100 parts by mass to prepare a liquid detergent composition. did. When (E) component and (F) component were used, they were added together with (D) component.
The pH is adjusted by adjusting the pH adjusting agent (potassium hydroxide (Asahi Glass Co., Ltd.) or sulfuric acid (Toho Zinc Co., Ltd.)) so that the pH at 25 ° C. of the liquid cleaning composition is the pH shown in Table 1. This was done by adding.

<Evaluation method>
About the liquid cleaning composition prepared in the present Example, the container depression | indentation suppression effect by oxygen absorption, the recontamination prevention effect, and external appearance stability were evaluated with the method and evaluation criteria shown below.
[Inhibition of container dents due to oxygen absorption]
15 g of the liquid detergent composition of each example is placed in a gas chromatography vial (GL Science, 125 × 22-CV T-617), and an aluminum cap (GL Science, 500 × 20-AC-ST3) is attached. And stored at 50 ° C. for 14 days. After storage, the gas in the headspace portion of the vial was collected, and the oxygen concentration was measured using a gas chromatograph (GC3200, manufactured by GL Sciences). The measurement conditions were an INJ temperature of 100 ° C., a sample injection amount of 0.1 mL, a DET temperature of 100 ° C., and an OVEN temperature of 50 ° C. From the measured oxygen concentration, the container depression suppression effect by oxygen absorption was evaluated based on the following criteria.
A: The oxygen concentration is 20% or more and 21% or less.
A: The oxygen concentration is 18% or more and less than 20%.
○: The oxygen concentration is 15% or more and less than 18%.
Δ: The oxygen concentration is 12% or more and less than 15%.
X: Oxygen concentration is less than 12%.

[Re-contamination prevention effect]
(Cleaning conditions)
Using a Terg-o-meter (manufactured by UNITED STATES TESTING), the liquid detergent composition is put in 900 mL of 3 ° DH hard water at 25 ° C. with the input amount shown in Table 1 and Table 2, and this is used as a recontamination determination cloth. 5 cotton knitted fabrics (manufactured by Tanigami Shoten), wet artificially contaminated cloth (made by Laundry Science Association, 28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin , 20 sheets of squalene 2.5%, cholesterol 1.6%, gelatin 7.0%, mud 29.8%, carbon black 0.5%), and fine skin shirt (LL size, manufactured by DVD) (3 × 3 cm or so) was put, and then the bath ratio was adjusted to 20 times with 3 ° DH hard water and washed at 120 rpm and 25 ° C. for 10 minutes.
(rinse)
The washed cloth was dehydrated for 1 minute, and then rinsed with 900 mL of 3 ° DH hard water at 25 ° C. for 3 minutes at 120 rpm and 25 ° C. This rinsing was repeated twice. The second time was performed by adding a predetermined amount of a softening agent. As the softener, room-dried saffron (manufactured by Lion) was used.
(Dry)
After the rinsed cloth was dehydrated for 1 minute, only the recontamination determination cloth was taken out and sandwiched between filter papers and dried with an iron.
This washing, rinsing and drying process was repeated three times. Evaluation is performed by measuring the reflectance of the recontamination determination cloth using a reflectometer (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) and calculating the Z value before and after cleaning. ΔZ, which is a value obtained by subtracting the Z value after washing from the previous Z value, was obtained, and the anti-staining effect was evaluated from the average value of the five sheets. The evaluation criteria are as shown below.
A: ΔZ is 4 or more and less than 6.
○: ΔZ is 6 or more and less than 8.
Δ: ΔZ is 8 or more and less than 10.
X: ΔZ is 10 or more.

[Appearance stability]
The liquid detergent composition of each example was allowed to stand at room temperature for 1 day after preparation, and then the appearance was visually observed and evaluated according to the following criteria.
A: Transparent and no change in appearance.
○: Appearance slightly turbid but not problematic.
X: Separated into two phases.
Table 1 and Table 2 show the evaluation of the liquid detergent composition of each example. In Tables 1 and 2, the unit of the content of each component is parts by mass, except for the input amount at the time of washing (the input amount of the liquid detergent composition in the cleaning for evaluating the anti-staining effect). . Moreover, the quantity of each component shows content as a pure part except a fragrance | flavor composition, and a fragrance | flavor composition is content as a composition.

As shown in Table 1 and Table 2, in the liquid detergent compositions of Examples 1 to 18 containing hydrogen peroxide as the component (D), the gas oxygen concentration in the head space of the vial is high, Oxygen absorption by the alkanolamine which is the component (C) was suppressed. Further, the effect of preventing recontamination and appearance stability were also excellent.
Further, when Examples 1, 2, 10 and 11 were compared, oxygen absorption by alkanolamine was suppressed with higher efficiency as the amount of hydrogen peroxide increased.
Further, when Examples 1, 12 and 13 were compared, the effect of preventing recontamination was higher as the amount of the linear alkylbenzene sulfonic acid as the component (B) was larger, and the appearance stability was better as the amount was smaller.
Moreover, in the liquid detergent composition of Examples 14-18, the effect which suppresses the oxygen absorption by alkanolamine was still higher by using (E) component and (F) component.

On the other hand, the liquid detergent composition of Comparative Example 2, which contains only the component (A), had a low anti-recontamination effect.
Although the liquid detergent composition of Comparative Example 4 in which the component (B) was used in addition to the component (A), the anti-staining effect was improved as compared with the liquid detergent of Comparative Example 1, the appearance stability was lowered. .
Although the liquid detergent composition of Comparative Example 1 containing the component (C) in addition to the component (A) and the component (B) has improved appearance stability compared to the liquid detergent of Comparative Example 4, By containing the component (C), oxygen absorption occurred and the oxygen concentration was lowered.
Moreover, also about the liquid cleaning composition of the comparative example 3 whose (A) component is 30 mass%, oxygen concentration became low by containing (C) component.

Claims (3)

(A) component: alkylene oxide adduct represented by the following formula (I); (B) component: linear alkylbenzene sulfonic acid; (C) component: alkanolamine; and (D) component: hydrogen peroxide. And a content of the component (A) is 50 to 70% by mass.

(However, R ¹ is a linear or branched alkyl group having 9 to 13 carbon atoms, or a linear or branched alkenyl group having 9 to 13 carbon atoms, and R ² is 2 to 2 carbon atoms. 4 is an alkylene group, R ³ is an alkyl group having 1 to ³ carbon atoms, and n is an integer of 5 to 30.)   Furthermore, (E) component: The liquid cleaning composition of Claim 1 containing a metal ion scavenger.   Furthermore, (F) component: The liquid cleaning composition of Claim 1 or 2 containing a phenol type radical scavenger.